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WO2025257072A1 - Pesticidally active 2-oxobenzimidazole compounds - Google Patents

Pesticidally active 2-oxobenzimidazole compounds

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Publication number
WO2025257072A1
WO2025257072A1 PCT/EP2025/065891 EP2025065891W WO2025257072A1 WO 2025257072 A1 WO2025257072 A1 WO 2025257072A1 EP 2025065891 W EP2025065891 W EP 2025065891W WO 2025257072 A1 WO2025257072 A1 WO 2025257072A1
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WO
WIPO (PCT)
Prior art keywords
methyl
formula
spp
oxo
benzimidazole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/065891
Other languages
French (fr)
Inventor
Jagadeesh Prathap KILARU
Andre Jeanguenat
Michel Muehlebach
Christopher Charles SCARBOROUGH
André Stoller
Rushil FERNANDES
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Syngenta Crop Protection AG Switzerland
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Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Publication of WO2025257072A1 publication Critical patent/WO2025257072A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/601,4-Diazines; Hydrogenated 1,4-diazines
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647Triazoles; Hydrogenated triazoles
    • A01N43/6531,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00Arthropodicides
    • A01P7/04Insecticides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00Antiparasitic agents
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D235/00Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/26Oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D403/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D417/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to pesticidally active 2-oxobenzimidazole compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active 2-oxobenzimidazole compounds.
  • the invention also relates to the preparation of these 2-oxobenzimidazole compounds, to intermediates useful in the preparation of these 2-oxobenzimidazole compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these 2-oxobenzimidazole compounds, to preparation of these compositions and to the use of these 2-oxobenzimidazole compounds or compositions in agriculture or horticulture, for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina.
  • BACKGROUND W O 2023/037249, WO 2023/285175 and WO 2019/197468 describe certain fused heterobicyclic carboxamide derivatives with pesticidal activity.
  • WO 2021/069567, WO 2021/069575, WO 2019/201835, and WO 2019/197468 describe some heteroaryI-triazole and heteroaryI- pyrazine compounds as pesticides.
  • WO 2025/045835, WO 2025/045837 and WO 2025/045838 also disclose heteroaryI-triazole and heteroaryI- pyrazine compounds as pesticides.
  • BRIEF SUMMARY [0003] It has now surprisingly been found that certain novel 2-oxobenzimidazole compounds have pesticidal activity. More specifically, certain novel 2-oxo-3H-benzimidazole-4-carboxamide compounds and aza analogues thereof, have pesticidal activity.
  • the present invention accordingly relates, in a first aspect, to a compound of the formula (I) wherein A is CH or N; X is oxygen or sulfur; the staggered line represents the connection of Q to the rest of compound of the formula (I); 109921
  • R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl;
  • R 2a is hydrogen, C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano;
  • R 2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloal
  • the present invention also provides a method of preparation of compounds of formula (I) as well as intermediate compounds useful in the preparation of compounds of formula (I).
  • the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient.
  • the present invention makes available a method for the protection of plant propagation material from the attack by a pest, such as insects, acarines, nematodes, or molluscs, which 109921
  • a pest such as insects, acarines, nematodes, or molluscs, which 109921
  • the propagation material or the site where the propagation material is planted with an effective amount of a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect.
  • a plant propagation material such as a seed, comprising, or treated with, or coated with, or adhered thereto, a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect.
  • the present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect.
  • the present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect.
  • the present invention further provides a method for preventing and/or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula (I) as defined in the first aspect, to an animal in need thereof.
  • Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1- C4alkane- or arylsulfonic acids
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor-pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor-pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-,
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • C1-Cnalkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- 109921
  • C1-Cnhaloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2- iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoro
  • C1-C2fluoroalkyl refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.
  • C1-Cnalkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy.
  • haloC1-Cnalkoxy refers to a C1-Cnalkoxy radical where one or more hydrogen atoms on the alkyl radical is replaced by the same or different halo atom(s) - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy.
  • C1-Cncyanoalkyl refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1- (cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.
  • C3-Cncycloalkyl refers to a saturated monocyclic hydrocarbon radical attached via any of the ring carbon atoms and having 3 to n carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cyanoC3-Cncycloalkyl refers to a C3-Cncycloalkyl where one of the hydrogen atoms in these radicals is replaced by a cyano group.
  • C3-C4cycloalkylC1-C2alkyl refers to a cyclopropyl or cyclobutyl radical bonded via a methylene or ethylene bridge to the rest of the molecule.
  • the substituent(s) can be bonded to the C3-C4cycloalkyl radical and/or to the C1-C2alkyl bridge.
  • C1-Cnalkylsulfanyl refers to a C1-Cnalkyl moiety linked through a sulfur atom.
  • C1-Cnhaloalkylthio or “C1-Cnhaloalkylsulfanyl” as used herein refers to a C1- Cnhaloalkyl moiety linked through a sulfur atom.
  • C3-Cncycloalkylsulfanyl refers to 3-n membered cycloalkyl moiety linked through a sulfur atom.
  • C2-Cnalkenyl refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl.
  • C2-Cnalkynyl refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.
  • Halogen or "halo" is generally fluorine, chlorine, bromine or iodine.
  • halogen in combination with other meanings, such as haloalkyl.
  • optionally substituted means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example, "C3-C4cycloalkyl is optionally substituted with 1 or 2 halogen atoms" means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halogen atom and C3-C4cycloalkyl substituted with 2 halogen atoms.
  • controlling refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
  • pest refers to insects and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest.
  • the term “effective amount” refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
  • an effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to 109921
  • compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in formula (I*) below: w here A, R1, R2a, R2b, R3, Q and X are as defined in the first aspect.
  • the present invention contemplates both racemates and individual enantiomers.
  • Compounds of formula (I') having a preferred stereochemistry are set out below: [0036]
  • Particularly preferred compounds of the present invention are compounds of formula (I’), where A, R1, R2a, R2b, R3, Q and X are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N- oxides of the compounds of formula (I’), and agrochemically acceptable salts thereof.
  • Particularly preferred compounds of formula (I’) include compounds of formula (I’a) as shown below, where X is oxygen, and A, R1, R2a, R2b, R3 and Q are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I*a), and agrochemically acceptable salts thereof:
  • Particularly preferred compounds of the present invention are compounds of formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a), where A is CH, X is oxygen, and where R1, R2a, R 2b , R 3 , and Q are as defined in the first aspect, as shown with compounds of formula (I*b) and (I’b) below: 109921
  • Embodiments according to the invention are provided as set out below.
  • A is N.
  • the moiety containing A is a 2-oxo-imidazo[4,5-b]pyridine group.
  • A is CH.
  • A is CH.
  • the moiety containing A is a 2- oxo-benzimidazole group.
  • X is oxygen (i.e. an oxygen atom).
  • X is S (i.e. a sulfur atom).
  • X is oxygen.
  • R1 is as follows: A. R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B . R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl; or C. R1 is hydrogen, methyl, or cyclopropylmethyl; or D. R1 is hydrogen or methyl; or E. R1 is methyl; or F. R1 is hydrogen.
  • R1 is hydrogen, methyl, or cyclopropylmethyl; or R 1 is hydrogen or methyl. Most preferably, R 1 is hydrogen.
  • R2a is as follows: A. R2a is hydrogen, C1-C3alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; or B .
  • R2a is hydrogen, C1-C3alkyl, C1-C3fluoroalkyl, cyclopropyl, cyclobutyl, or cyclopropyl substituted with a single fluoro or cyano; or C .
  • R2a is C1-C3alkyl, C1-C3fluoroalkyl, cyclopropyl, or cyclopropyl substituted with a single fluoro or cyano; or D .
  • R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; or E.
  • R2a is methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; or F. R2a is methyl, ethyl, or cyclopropyl; or G. R2a is methyl or cyclopropyl; or H. R2a is cyclopropyl. 109921
  • R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl.
  • R 2a is methyl, ethyl, or cyclopropyl.
  • R 2a is cyclopropyl.
  • R2b is as follows: A. R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3- C 4cycloalkylcarbonyl, or C3-C4cyclo
  • R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfonyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, cyclopropyl, or cyclopropyl substituted with one or two substituents independently selected from the group consisting of halogen, cyano, methyl, and trifluoromethyl; or C .
  • R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl; or D .
  • R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, or cyclopropyl; or E .
  • R2b is halogen, C1-C3fluoroalkyl, C1-C3fluoroalkoxy, C1-C3fluoroalkylsulfonyl, or cyclopropyl; or F. R2b is halogen, C1-C3fluoroalkyl, C1-C3fluoroalkoxy, or cyclopropyl; or G. R2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; or H .
  • R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl; or I. R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; or J . R2b is chloro, bromo, difluoromethyl, trifluoromethyl, or cyclopropyl; or K. R2b is chloro, difluoromethyl, or cyclopropyl; or L. R2b is trifluoromethyl; or M.
  • R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, trifluoromethyl, or difluoromethoxy; or N.
  • R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, or cyclopropyl; or O .
  • R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, or cyclopropyl; or P.
  • R2b is chloro, trifluoromethyl, difluoromethoxy, or cyclopropyl; or Q.
  • R2b is trifluoromethyl or difluoromethoxy; or R.
  • R2b is difluoromethyl, trifluoromethyl, or difluoromethoxy. [0047] In preferred embodiments of each aspect of the invention, R2b is halogen, C1-C3fluoroalkyl, C1- C3fluoroalkoxy, or cyclopropyl.
  • R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; such as R 2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, trifluoromethyl, or difluoromethoxy, or R 2b is chloro, bromo, 109921
  • R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, or difluoromethoxy, or cyclopropyl, or R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, or cyclopropyl; such as R2b is chloro, trifluoromethyl, difluoromethoxy, or cyclopropyl, or R2b is chloro, difluoromethyl, or cyclopropyl.
  • R2b is difluoromethyl, trifluoromethyl, or difluoromethoxy
  • R2b is trifluoromethyl or difluoromethoxy.
  • R3 is as follows: A. R3 is C1-C3alkyl or C1-C3haloalkyl; or B. R3 is methyl or trifluoromethyl; or C. R3 is methyl. [0049] In preferred embodiments of each aspect of the invention, R3 is methyl. [0050] In an embodiment of each aspect of the invention, Q is Qa. In embodiments where Q is Qa, R5 is as follows: A . R5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkyloxy, or C3-C4cycloalkyl; or B.
  • R5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or C. R5 is hydrogen, halogen, C1-C3alkyl, or C1-C3alkyloxy; or D. R5 is hydrogen, halogen, or C1-C3alkyloxy; or E. R5 is hydrogen, halogen, or C1-C3alkyl; or F. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, or ethoxy; or G.
  • R5 is hydrogen, chloro, bromo, methyl, ethyl, cyclopropyl, methoxy, or ethoxy; or H.
  • R5 is hydrogen, bromo, iodo, methyl, cyclopropyl; or I.
  • R5 is hydrogen, chloro, bromo, iodo, methoxy, or ethoxy; or J.
  • R5 is hydrogen, bromo, iodo, or cyclopropyl; or K.
  • R5 is hydrogen, chloro, bromo, iodo, methyl, or ethyl; or L.
  • R5 is hydrogen, chloro, bromo, or methyl; or M.
  • R5 is hydrogen, chloro, or bromo; or N.
  • R5 is hydrogen; or O.
  • R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy
  • R5 is hydrogen, chloro, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, or ethoxy; such as R 5 is hydrogen, chloro, bromo, methyl, ethyl, cyclopropyl, or methoxy.
  • R5 is hydrogen.
  • Qa is selected from Qa-1, Qa-2, Qa-3, Qa-4, Qa-5, or Qa-6; Qa is selected from Qa-1, Qa- 3, Qa-4, Qa-5, Qa-6, or Qa-7; or Qa is selected from Qa-1, Qa-5, or Qa-6.
  • Q is Qa-1: 109921
  • R5a and R5b are as follows: A. R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkyloxy, or C3-C4cycloalkyl; or B.
  • R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or C. R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, or C1-C3alkyloxy; or D. R5a and R5b are independently hydrogen, halogen, or C1-C3alkyloxy; or E. R5a and R5b are independently hydrogen, halogen, or C1-C3alkyl; or F. R5a and R5b are independently hydrogen, fluoro, chloro, bromo, iodo, methoxy, or ethoxy; or G.
  • R5a and R5b are independently hydrogen, fluoro, chloro, bromo, iodo, or cyclopropyl; or H.
  • R5a and R5b are independently hydrogen, fluoro, chloro, bromo, iodo, methyl, or ethyl; or I.
  • R5a and R5b are independently hydrogen, fluoro, chloro, bromo, methyl, ethyl, cyclopropyl, methoxy, or ethoxy; or J .
  • R5a and R5b are independently hydrogen, fluoro, chloro, methyl, cyclopropyl, or methoxy; or K.
  • R5a and R5b are independently hydrogen, methyl, cyclopropyl, or methoxy; or L. R5a and R5b are differently hydrogen, chloro, methyl, cyclopropyl, or methoxy; or M. R5a or R5b is hydrogen, and the other is hydrogen, fluoro, chloro, methyl, cyclopropyl, or methoxy; or N. R5a and R5b are both hydrogen or fluoro; or O. R5a and R5b are hydrogen. [0054] In preferred embodiments where Q is Qb: A. R5a is hydrogen, chloro, fluoro, cyclopropyl, or methoxy; and R5b is hydrogen, fluoro, or methoxy; or B.
  • R5a is hydrogen, fluoro, or cyclopropyl; and R5b is hydrogen, chloro, fluoro, or methoxy; or C.
  • R5a is hydrogen, fluoro, or cyclopropyl; and R5b is hydrogen, fluoro, or methoxy; or D.
  • R5a is hydrogen, fluoro, or cyclopropyl; and R5b is hydrogen; or 109921
  • R5a is hydrogen; and R5b is hydrogen, fluoro, or methoxy; or F.
  • R5a and R5b are hydrogen.
  • Qb is selected from Qb-1 to Qb-10: [0056] As an example, Qb is selected from Qb-1, Qb-2, Qb-3, Qb-5, Qb-6, Qb-7, Qb-8, Qb-9, or Qb-10. Preferably, Q b is selected from Q b -1, Q b -3, Q b -5, Q b -6, Q b -7, Q b -9, or Q b -10; such as Q b is selected from Q b -1, Q b -3, Q b -5, Q b -7, Q b -9, or Q b -10. Most preferably, Q b is Q b -1.
  • R4 is as follows: A. R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R 4b ; or R 4 is oxo-pyridazinyl optionally N- s ubstituted with a single substituent R4c; or 109921
  • R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6- cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5- b romopyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5- carbamoyl-thia
  • R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3- yl, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; or H .
  • R4 is 5-cyano-2-pyridyl, or pyrimidin-2-yl; or I.
  • R4 is 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, or 6-(methoxycarbonylamino)pyrimidin-4-yl; or J .
  • R4 is Qc-9, preferably 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; or K.
  • R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, or 5-cyanothiazol-2-yl; or L.
  • R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5- chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 6-methoxypyridazin-3-yl, 5- carbamoylpyrazin-2-yl, 1-methyl-6-o
  • R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4- yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl,
  • R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2-yl; or O .
  • R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl,5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5- bromopyrazin-2-yl, 5-carb
  • R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6- oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl.
  • R4 is Qc-1, Qc-2, Qc-3, or Qc-9. More preferably, R 4 is Q c -1, Q c -2, or Q c -9.
  • R 4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2- yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyra
  • R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, or Qc-9
  • R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl,5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl,
  • R 4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo- pyridazin-3-yl, or 5-cyanothiazol-2-yl.
  • R4a is as follows: 109921
  • R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R 4b ; or R 4a is oxo- p yridazinyl optionally N-substituted with a single substituent R4c; or B.
  • R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, Qc-9, Qc-10, or Qc-11: C .
  • R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, or Qc-9; or D.
  • R4a is Qc-1, Qc-2, or Qc-9; or E.
  • R4a is Qc-1; or F.
  • R4a is 5-cyano-2-pyridyl, pyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3- y l, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; or G.
  • R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl; or H. R4a is 5-cyano-2-pyridyl.
  • R4a is Qc-1, Qc-2, Qc-3, or Qc-9, such as R 4a is Q c -1, Q c -2, or Q c -9. More preferably, R 4a is Q c -1.
  • the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, and oxo-pyridazinyl rings of R 4 and R 4a are each connected to the remainder of the compound via a carbon atom.
  • a carbon atom of the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, or oxo-pyridazinyl rings of R 4 and R 4a is linked to Q a or Q b , respectively.
  • R4b is as follows: A.
  • R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR 10 R 11 , -N(R 11 )C(O)OR 10 , or -N(R 11 )C(O)R 10 ; or B .
  • R4b is hydrogen, halogen, cyano, hydroxy, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1- C3fluoroalkoxy, -C(O)NR 10 R 11 , or -NHC(O)R 10 ; or 109921
  • R4b is hydrogen, fluoro, chloro, iodo, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10 or - N(CH3)C(O)R 10 ; or D .
  • R4b is hydrogen, chloro, iodo, cyano, C1-C3alkyl, methoxy, -C(O)NR10R11, -NHC(O)R10 or - N(CH3)C(O)R 10 ; or E .
  • R4b is hydrogen, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10 or -N(CH3)C(O)R10; or F.
  • R4b is hydrogen, cyano, C1-C3alkyl, methoxy, -C(O)NHR11, -NHC(O)R10 or -N(CH3)C(O)R10; or G.
  • R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, - NHC(O)R 10 or -N(CH3)C(O)R 10 ; or H .
  • R4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, - C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or I .
  • R4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or J. R4b is hydrogen, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or K. R4b is hydrogen, cyano, -C(O)NH2, or -C(O)NHCH3; or L. R4b is hydrogen or cyano; or M. R4b is cyano, -C(O)NH2, or -C(O)NHCH3; or N. R4b is hydrogen; or O.
  • R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, - C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or P .
  • R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, - C(O)N(CH3)R 11 , -NHC(O)R 10 or -N(CH3)C(O)R 10 ; or Q .
  • R4b is hydrogen, fluoro, chloro, bromo, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or R. R4b is hydrogen, fluoro, chloro, bromo, cyano, or -C(O)NH2; or S. R4b is hydrogen, fluoro, chloro, bromo, cyano, difluoromethyl, methoxy, or -C(O)NH2. [0064] In an embodiment of each aspect of the invention, for instance where Q is Qa-1 or Qb-1, R10 is as follows: A .
  • R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or B.
  • R10 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, cyclopropylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or C.
  • R10 is hydrogen, C1-C3alkyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, cyanoC3- C4cycloalkyl, or C1-C3alkoxyC1-C3alkyl; or D .
  • R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; or E .
  • R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or cyanomethyl; or F.
  • R10 is hydrogen, methyl, ethyl, isopropyl, or cyclopropyl; or G.
  • R10 is hydrogen, methyl, or cyanomethyl; or H.
  • R10 is hydrogen or methyl and R 11 is as follows: 109921
  • R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or B .
  • R11 is hydrogen, hydroxy, C1-C3alkyl, C1-C3cyanoalkyl, cyanoC3-C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C3alkoxy; or C .
  • R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, C1-C3cyanoalkyl, or C1-C3alkoxy; or D. R11 is hydrogen, C1-C3alkyl, cyanocyclopropyl, C1-C3alkoxyC1-C3alkyl, or methoxy; or E. R11 is hydrogen, C1-C3alkyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, or C1-C3alkoxy; or F. R11 is hydrogen, C1-C3alkyl, cyclopropyl, or C1-C3alkoxy; or G.
  • R11 is hydrogen, C1-C3alkyl, cyclopropyl, or methoxy; or H. R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; or I . R11 is hydrogen or methyl; or J. R11 is hydrogen. [0065] In preferred embodiments of each aspect of the invention, R10 is hydrogen, methyl, or cyanomethyl, such as R 10 is hydrogen or methyl. Also in embodiments of each aspect of the invention, R 11 is hydrogen or methyl, such as R 11 is hydrogen.
  • R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or - NHC(O)OCH3; or R 4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, - C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3.
  • R 4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or R4b is hydrogen, fluoro, chloro, bromo, cyano, or -C(O)NH2.
  • R 4b is hydrogen, fluoro, chloro, bromo, cyano, difluoromethyl, methoxy, or -C(O)NH2.
  • the group R4b is in the meta or para position with respect to the link of R 4 or R 4a to the remainder of the compound, i.e. to the Q a or Q b ring, respectively.
  • R4c is as follows: A. R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; or B. R4c is C1-C3alkyl, C1-C3haloalkyl, or C3-C6cycloalkylC1-C4alkyl; or C. R4c is methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl, or cyclopropylmethyl; or D .
  • R4c is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl; or E. R4c is methyl, ethyl, or cyclopropylmethyl; or F. R4c is methyl or cyclopropylmethyl; or G. R4c is methyl or ethyl; or H. R4c is methyl. [0069] In preferred embodiments of each aspect of the invention, R4c is methyl or ethyl. For instance, R4c is methyl.
  • R4 and R4a are selected from QQ-1 to QQ-24, where the staggered line represents the connection to Qa or Qb: 109921
  • R4 and R4a are selected from QQ-1, QQ-2, QQ-3, QQ-4, QQ-5, QQ- 6, QQ-7, QQ-8, QQ-9, QQ-10, QQ-11, QQ-12, QQ-13, QQ-15, QQ-18, QQ-19, QQ-20, and QQ-21; or R4 and R 4a , as the case may be, are selected from QQ-1, QQ-2, QQ-3, QQ-4, QQ-5, QQ-6, QQ-7, QQ-8, QQ-9, QQ- 10, QQ-11, QQ-12, QQ-13, and QQ-15.
  • R 4 and R 4a are selected from QQ-1, QQ-2, QQ-9, Q Q-18, QQ-19, QQ-20, and QQ-21; or R4 and R4a are selected from QQ-1, QQ-2, and QQ-9. Still preferably, R 4 and R 4a , as the case may be, are selected from QQ-1, QQ-2, QQ-3, QQ-5, QQ-9, QQ-13, QQ-15, QQ-18, QQ-19, QQ-20, QQ-21, QQ-22, QQ-23, and QQ-24.
  • a preferred group of compounds of formula (I) is represented by compounds of formula (I-A): w herein A, R1, R2a, R2b and Q are as defined for compound of formula (I); or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula (I-A). More preferably, A is CH. [ 0073] Accordingly, the present invention makes available a compound of formula (I) having the substituents A, Q (i.e.
  • A is CH or N
  • X is an oxygen atom or a sulfur atom
  • Q is Qa or Qb
  • R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl
  • R 2a is hydrogen, C1-C4alkyl, C1- C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano
  • A is CH or N;
  • X is oxygen or sulfur;
  • R1 is hydrogen, methyl, or cyclopropyl-methyl;
  • R 2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1- cyanocyclopropyl;
  • R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl;
  • R 3 is methyl;
  • Q is Q a ;
  • R 4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2
  • A is CH or N;
  • X is oxygen or sulfur;
  • R1 is hydrogen, methyl, or cyclopropyl-methyl;
  • R 2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1- cyanocyclopropyl;
  • R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl;
  • R 3 is methyl;
  • Q is Q a ;
  • R 4 is pyrimidin-2-yl, 5- cyano-2-pyridyl, or 5-cyanothiazol-2-yl; and
  • R 5 is hydrogen.
  • compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, methyl, or cyclopropyl-methyl; R 2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1- cyanocyclopropyl; R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R 3 is methyl; Q is Q a ; R 4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2-y
  • compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, or methyl; R 2a is hydrogen, methyl, ethyl, cyclopropyl; R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R 3 is methyl; Q is Q a ; R 4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5- chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2-yl; and R 5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or meth
  • A is CH; X is oxygen; R1 is hydrogen, or methyl; R 2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; R 2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R 3 is methyl; Q is Q a ; R 4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, or 5- cyanothiazol-2-yl; and R 5 is hydrogen.
  • T represents have the same meaning as given for compounds of formula (I), and the staggered line represents the connection to the remainder of the compounds where T is attached to, such as the compounds of the formula (I), (Ia), (Ia-1), (Ib), (II), (IV), (IVa), (X), (XI) in Schemes 1 to 6
  • Compounds of the formula (I) can be made, for example, by reaction of a compound of the formula (II), wherein X1 is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride or fluoride, and wherein T has the meaning given above, with a compound of formula (III), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other 109921
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®).
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium
  • T3P® propanephosphonic acid cycl
  • Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N
  • compounds of the formula (II) are either known, or they can be prepared by methods known to a person skilled in the art.
  • compounds of the formula (II) wherein X1 is a leaving group, such as a halogen, for instance chloride or fluoride can be formed by treatment of compounds of formula (II) wherein X 1 is hydroxy with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), or a fluorinating agent, like diethylaminosulfur trifluoride (DAST), bis(2-methoxyethyl)aminosulfur trifluoride (deoxofluorTM) or 2,4,6- trifluoro-1,3,5-triazine, in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • an organic base such as, for example, triethylamine.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid
  • a Lewis acid such as zinc bromide or titanium(IV) isopropoxide
  • compounds of formula (I) can be made, for example, by reaction of compound of the formula (IV), wherein T has the same meaning as given above in Scheme 1, and R 1 has the same meaning as given above for compounds of the formula (I), with a compound of the formula (V), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), and X 2 is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • organic base such as, for example, triethylamine.
  • a compound of the formula (I) can be made by reaction of a compound of the formula (IVa), wherein T has the same meaning as given above in Scheme 1, with a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I).
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, 109921
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon, 109921
  • an acid such as acetic acid
  • a Lewis acid such as zinc bromide
  • This reaction is done with or without a solvent, preferably in a solvent, with or without an additive, such as a radical starter, such as, for example, benzoyl peroxide or azoisobutyronitrile.
  • a radical starter such as, for example, benzoyl peroxide or azoisobutyronitrile.
  • the reaction can be done with or without exposure to visible light, or to UV light, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I) can be treated with a reducing agent, followed by reaction with a sulfonyl chloride, for instance methanesulfonyl chloride, to give a compound of the formula (V), wherein the leaving group X 2 is a sulfonate, for instance a mesylate.
  • This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a base such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • the reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a compound of the formula (Ia), wherein T has the same meaning as given above in Scheme 1, and R3 and Q have the same meaning as given above for compounds of the formula (I), can be reacted with a compound of the formula (VI), wherein R 1 has the same meaning as given above for compounds of the formula (I), except that R 1 is different from hydrogen, and wherein X 30 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula (Ia-1).
  • a leaving group such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 100 °C, or between ambient temperature and 50 °C, without a base or in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane
  • a base such as an inorganic base, for instance sodium, potassium or cesium carbonate
  • an organic base such as, for example, triethylamine, diisopropylethylamine
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid, in a temperature 109921
  • the intermediate compounds of formula (X) and of formula (XI) can be used as crude products for the subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation.
  • Compounds of the formula (Ik) can be prepared by the reaction of an amine of the formula (IIIf), or a salt thereof w herein R1, R3, R4 and R5 are as described in formula (I), with a compound of the formula (IIa) w herein A, R2a and R2b are as described in formula (I) and X1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride or fluoride, under conditions already described in Scheme 1. 109921
  • Compounds of formula (Ic) can be made, for example, as shown in scheme 7.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid, or a Lewis acid, such as zinc bromide
  • a solvent or without a solvent such as, for instance, methanol.
  • R4a-M1 is a metal, such as for instance lithium, or –MgCl, or –ZnBr, or –B(OH)2; or R4a-M1 represents a boronate, such as a pinacol ester of a boronic acid, or a stannane such as R4a-Sn(n-Bu)3.
  • Such transformations are known to a person skilled in the art as Suzuki-, Kumada-, 109921
  • Such reactions are carried out in a temperature range of - 100 to +300 °C, preferably between ambient temperature and 200 °C, in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst (for example palladium(II) acetate, 1,1’- bis(diphenylphosphino)ferrocene-palladium(II)dichloride or tetrakis(triphenyl-phosphine)palladium(0)), and optionally in the presence of an additional ligand, such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand.
  • a catalyst such as a metal catalyst, for instance a palladium catalyst (for example pal
  • the reaction can be done in the presence or absence of an additional metal catalyst, such as, for example, a copper salt, for instance CuI.
  • a base which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or tribasic potassium phosphate, or an organic base, such as an amine base, for instance triethyl amine.
  • This reaction is done with or without a solvent, preferentially in a solvent, such as tetrahydrofuran, 2- methyltetrahydrofuran, acetonitrile, toluene or N,N-dimethylformamide, optionally in the presence of water.
  • reaction can be conducted under microwave irradiation or with conventional heating, such as heating the reaction vessel in an oil bath.
  • compound (XVII) can be reacted with a compound of the formula (XV) to give intermediate (XVIII).
  • This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate (XIV) to the compound of formula (Ic).
  • the intermediate (XVIII) is reacted with a compound of the formula (IVb) to give a compound of the formula (Ic), wherein R1 is hydrogen and A, R2a, R2b, R3 and R4a have the same meaning as given above for compounds of the formula (I).
  • the intermediate of the formula (IIIa), or a salt thereof is reacted with a compound of the formula (IIa) to give the compound of the formula (Ic), wherein A, R2a, R2b, R1, R3 and R4a have the same meaning as given above for compounds of the formula (I).
  • This reaction is done essentially under the same conditions as described above for the transformation of intermediate (XVI) to intermediate (XIV).
  • the intermediate compounds of formulas (XIV), (XVI), (XVIII) and (IIIa) can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation.
  • Compounds of the formula (XVII) are known, or they can be prepared by methods known to a person skilled in the art.
  • 83192 FF can be prepared by the reaction of an amine of the formula (IIIb), or a salt thereof w herein R1, R3, R4a, R5a and R5b are as described in formula (I), with a compound of the formula (IIa) w herein A, R2a and R2b are as described in formula (I) and X1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride or fluoride, under conditions already described in Scheme 1.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such 109921
  • a solvent such as an organic solvent, for instance acetonitrile
  • Amines of formula (IIIc), or a salt thereof may be obtained by biocatalyzed deracemization of amines of formula (IIId), or a salt thereof. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • compounds of formula (IIIc), or a salt thereof can be obtained from compounds of the formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I), following the synthesis described in Scheme 10.
  • Such intermediates of formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXI), wherein R3, R4a, R5a, and R5b are as described in formula (I), by a Mitsunobu reaction, which involves treating alcohols of formula (XXI) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine, such as triphenylphos
  • Alcohols of formula (XXI) may be obtained by enantioselective reduction of ketones of formula (XXIV), wherein R3, R4a, R5a, and R5b are as described in formula (I).
  • reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • Amines of formula (XXV) can be obtained by condensation of diamines of formula (XLVII), wherein R5a, and R5b are as described in formula (I), on diketones of formula (XXVI), wherein R3 and R4a are as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ.
  • Diketones of formula (XXVI) may be formed by oxidation of hydroxyketones of formula (XXVII), wherein R3 and R4a are as described in formula (I).
  • This oxidation can involve for instance SO3-pyridine in presence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/Bu4NHSO4.
  • solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof
  • base for instance triethylamine or alternatively sodium hypochlorite
  • a catalyst such as TEMPO/Bu4NHSO4.
  • Hydroxyketones of formula (XXVII) may be synthesized by cross-benzoin condensation between aldehydes of formula (XXIX), wherein R4a is as described in formula (I), and aldehydes of formula (XXVIII), wherein R 3 is as described in formula (I).
  • Aldehydes of formula (XXVIII) are commercially available in chiral form, like for instance Boc-L- alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36- 9).
  • Cross-benzoin condensations are done in the usual way by employing an organocatalyst such as a triazolium salt or a thiazolium salt, in the presence of a base such as potassium tert-butoxide or N,N- isopropylethylamine, in a suitable solvent such as DCM or THF, at a temperature between -20 °C and the 109921
  • a base such as potassium tert-butoxide or N,N- isopropylethylamine
  • a suitable solvent such as DCM or THF
  • compounds of formula (Id) can be alternatively prepared by reaction of compounds of formula (XXX) (wherein A, R2a, R2b, R1, R3, R5a and R5b are as defined in formula (I) and X07 is a leaving group like, for example, chlorine, bromine, iodine) with compounds of formula (XXXI) (Stille reaction; R4a in XXXI is as defined in formula I) or compounds of formula (XXXII) (Suzuki-Miyaura reaction; R4a in XXXII is as defined in formula (I) and W is a boronic acid B(OH)2 group, or a corresponding boronate, such as a pinacol ester of said boronic acid) in the presence of a palladium catalyst as described in detail in Scheme 7.
  • Amines of formula (XXXIV) can be prepared by deracemization procedure method, which involves for example, a selective acylation of one enantiomer.
  • 83192 FF formula (XXXVI) are for instance mandelic acid or (1R)-menthylchloroformate.
  • Intermediates of formula (XXXVII) can be formed by coupling of a chiral auxiliary of formula (XXXVI), wherein X0 is a leaving group, such as chlorine, with amines of the formula (XXXIVa) following the conditions detailed in Scheme 1. Examples of such deracemization processes are reported in the literature, for instance in J. Org. Chem.2007, 72, 485-493.
  • Amines of formula (XXXIV), or a salt thereof may be obtained from intermediates of formula (XXIIa), wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (when Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (when Z3 is -NBoc2), under deprotection conditions known to a person skilled
  • Such intermediates of formula (XXIIa), wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXIa), wherein R 3 , R5a, and R5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction, which involves treating alcohols of formula (XXIa) with an azodicarboxylate, such as diethyl azodicarbox
  • amines of formula (XXXIV) may be obtained by reduction of azides of formula (XXIIIa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or 109921
  • Azides of formula (XXIIIa) may be obtained by treatment of alcohols of formula (XXIa) with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • Alcohols of formula (XXIa) may be obtained by enantioselective reduction of ketones of formula (XXIVa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide.
  • Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p- cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • catalysts for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p- cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • compounds of the formula (I’a), a subset of compounds of the formula (I), wherein A, R1, R2a, R2b, R3 and Q are as defined for compounds of the formula (I), can be prepared by reaction of compounds of the formula (IIa-1), a subset of compounds of the formula (II) wherein A, R2a and R2b are as described in formula (I) and X1 is hydroxy, with either compounds of the formula (IIIf) or (IIIb), or a salt thereof, under conditions already described above (transformations IIa + IIIf to Ik, and IIa + IIIb to Id) and in Scheme 1.
  • Compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I), can be prepared by saponification of compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under conditions known to a person skilled in the art (using for example conditions such as: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane at room temperature, or up to refluxing conditions; or alternatively treating compounds of the formula (IIa-2) with an acid, such as for example a hydrohalide acid, preferably hydrochloric or hydrobromic acid, or trifluoroacetic acid, optionally in presence of a solvent, such as tetrahydrofuran, dioxane or dichloromethane, at temperatures between 0°C and
  • Compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by means of a carbonylation reaction on compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), in the presence of an alcohol R a OH, wherein R a is C1-C6alkyl or benzyl.
  • the compounds of formula (XL) are reacted with carbon monoxide CO (usually under pressure, for example in the range of 5 to 200 bar), in the presence 109921
  • a metal catalyst such as a palladium catalyst (for example: palladium(II) a
  • compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I) can be prepared by i. performing a lithium-halogen (Li-X3) exchange on compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), followed by ii. quenching the formed organolithium species with carbon dioxide.
  • Li-X3 lithium-halogen
  • Such lithium-halogen exchange reactions can be performed using, for example, organolithium compounds such as butyllithium (BuLi), in an anhydrous aprotic solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran or N,N′-dimethylpropylene-urea (DMPU), and at temperatures ranging from -120°C to 0°C, preferably between -78 and 0°C.
  • the formed lithiated intermediate is preferably quenched in situ with carbon dioxide (gaseous, or alternatively solid carbon dioxide known as dry ice) to generate the compounds of the formula (IIa-1). Similar reactions are reported in literature for example in WO 2006/013048.
  • Scheme 17 [0143] As shown above in Scheme 17, compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by treating compounds of the formula (L), wherein A, R2a and R 2b are as described in formula (I), with a halogenation reagent, for example, just to cite a few common reagents, N-chloro succinimide, N-bromo succinimide or N-iodo succinimide. Other halogenation reagents can also be used, as for example bromine.
  • a halogenation reagent for example, just to cite a few common reagents, N-chloro succinimide, N-bromo succinimide or N-iodo succinimide.
  • Other halogenation reagents can also
  • the reaction can be performed in an inert solvent like acetonitrile or acetic acid at a temperature usually comprised between 0°C and 80°C.
  • a stronger acid like trifluoroacetic acid, can facilitate the reaction.
  • 83192 FF Compounds of formula (L) can be obtained by cyclization of compounds of formula (LI), wherein A, R2a and R2b are as described in formula (I).
  • a cyclic urea is formed from two neighboring amino groups.
  • reagents like phosgene, diphosgene, triphosgene or carbonyl diimidazole, for example, can be used.
  • the reaction can usually be performed around.0°C to ambient temperature or at higher temperature for di- and triphosgene, in an inert anhydrous solvent, like toluene, ethyl acetate or chloroform.
  • the compounds of formula (LI) in turn, can be obtained by reduction of the nitro group of compounds of the formula (LII), wherein A, R2a and R2b are as described in formula (I). Nitro to amino reduction is very common in organic synthesis and can be performed under a multitude of conditions.
  • Compounds or the formula (LII) can be prepared by reacting compounds of the formula R2a-NH2 (LIV), or a salt thereof, wherein R2a is as described in formula (I), with compounds of the formula (LIII), wherein A and R2b are as described in formula (I) and X4 is a leaving group, like, for example a halogen atom, preferably bromine, chlorine or iodine (even more preferably chlorine).
  • X 4 can also be a leaving group like a sulfonate, for example a triflate, or an alkylsulfonyl or arylsulfonyl group, like Me-SO2- or benzenesulfonyl.
  • This reaction can be performed with an excess of (LIV), acting as a base or in presence of another non-reactive base, like Hünig’s base or triethylamine or a carbonate, like cesium carbonate or a phosphate, like trisodium phosphate or in the presence of a metal hydride, like sodium hydride. This substitution is facilitated by the presence of the neighboring nitro group.
  • another non-reactive base like Hünig’s base or triethylamine or a carbonate, like cesium carbonate or a phosphate, like trisodium phosphate or in the presence of a metal hydride, like sodium hydride.
  • compounds of the formula (IIA-1), wherein R2a and R2b are as defined in formula (I) may be obtained from compounds of the formula (LV), wherein R 2a and R 2b are as defined in formula (I) and Ar is an aromatic group, preferably phenyl, 4-tolyl, 4-chlorophenyl or 4-bromophenyl, under oxidative conditions, for example, aqueous potassium permanganate.
  • the compounds of formula (LV) can be obtained from the reaction of compounds of the formula (LVI), wherein R 2a and R 2b are as defined in formula (I) and Ar is an aromatic group as defined hereabove.
  • the cyclization can be performed with a wide variety of reagents, for example phosgene, diphosgene, triphosgene or carbonyl diimidazole.
  • the reaction is usually performed in an aprotic solvent, like toluene or a chlorinated hydrocarbon, like chloroform, dichloromethane, 1,2-dichloroethane.
  • a base as for example triethylamine or 4-dimethylaminopyridine, might be desirable, especially if there is formation of an acid as byproduct.
  • the reaction can be performed between 0°C and the boiling temperature of the reaction mixture, depending on the reactivity of the reagent used.
  • This protecting group depending on its nature, can be removed under acidic conditions, like trifluoroacetic acid or catalytic reduction (hydrogen over palladium on carbon, for example), or oxidative conditions. It might even be advantageous to perform the deprotection and the nitro reduction of compounds of the formula (LVIII) to yield in one step compounds of the formula (LVI).
  • the compounds of the formula (LVIII), as described hereabove can be obtained by reacting compounds of formula (LIX), wherein R2a and R2b are as defined in formula (I) and PG is a protecting group as described hereabove, with a compound of the formula (LXII), wherein Ar is an aromatic group as defined hereabove.
  • This type of reaction is called vicarious nucleophilic substitution and is performed with an excess of a strong base, often powdered potassium hydroxide or t-BuOK, in a polar solvent, like dimethyl sulfoxide or 109921
  • the compounds of the formula (LIX), wherein R2a and R2b are as defined in formula (I) and PG is a protecting group as described hereabove, can be obtained by derivatizing the nitrogen atom of compounds of the formula (LX), wherein R2a and R2b are as defined in formula (I).
  • Preferred methods are using a base in presence of an optionally substituted benzylic halide or sulfonate, for benzyl or 4-methoxybenzyl introduction (given as examples) or for reacting with chloromethyl methyl ether, or under acid catalysis with dihydrofuran or dihydropyran.
  • Compounds of formula (LX), wherein R2a and R2b are as defined in formula (I), can be prepared by reacting compounds of the formula (LXI), wherein R2b is as defined in formula (I) and X5 is a leaving group, as for example a halide, preferably fluoride or chloride, or a sulfonate, like triflate, mesylate or tosylate with an amine compounds of formula (LIV), or a salt thereof, wherein R2a is as defined in formula (I).
  • the leaving group X 5 is activated towards nucleophilic substitution by the neighboring nitro group.
  • This reaction is preferably performed in presence of a base like sodium hydride or cesium carbonate, in a solvent like dimethylformamide or acetonitrile, at temperatures comprised between 0°C and the boiling point of the reaction mixture, preferably around room temperature.
  • a base like sodium hydride or cesium carbonate
  • a solvent like dimethylformamide or acetonitrile
  • compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above wherein R 1 , R 3 , R 4a , R 5a and R 5b are as described in formula (I), particularly those compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above, wherein R 3 and R 4a are as described in formula (I) and in which R 1 , R5a and R5b are hydrogen, can be prepared in analogy to descriptions found for example in WO 2021/083936, WO 2021/069575, and WO 2022/258481.
  • 83192 FF or methyl and R 5 is hydrogen, methyl or cyclopropyl, can be prepared in analogy to descriptions found for example in WO 2021/083936, WO 2021/099303, WO 2021/105091, WO 2021/165195, WO 2021/224323, WO 2022/268648, WO 2023/104714 and WO 2023/247360.
  • compounds of the formula (IIIg), wherein R1, R3, R5, R10 and R11 are as described in formula (I) can be prepared according to reactions outlined in Scheme 20.
  • Scheme 20 [0159] As shown in Scheme 20, compounds of the formula (IIIg), wherein R1, R3, R5, R10 and R11 are as described in formula (I), can be prepared from compounds of formula (IIIg-1), wherein R1, R3, R5, R10 and R11 are as described in formula (I), and X- is an anion, by treatment with a base, such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin.
  • a base such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin.
  • the anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic 109921
  • an acid such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like
  • an organic acid such as a carboxylic 109921
  • Compounds of formula (IIIg-1), wherein R1, R3, R5, R10 and R11 are as described in formula (I), and X- is an anion can be made from compounds of the formula (IIIg-2), wherein R1, R3, R5, R10 and R11 are as described in formula (I), by treatment with an acid, such as the acids listed above.
  • the reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents.
  • trans-cyclohexyldiamine) or 1,10-phenanthroline optionally in the presence of a base, such as sodium, potassium or cesium carbonate, or potassium phosphate, in inert solvents such as alcohols, amides, esters, ethers, nitriles and water, particularly preferred are methanol, ethanol, 2,2,2- trifluoroethanol, propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, water or mixtures thereof, at temperatures between 0-150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally under microwave irradiation or pressurized conditions using an autoclave.
  • a base such as sodium, potassium or cesium carbonate, or potassium phosphate
  • H2NR11 is ammonia
  • ammonium hydroxide solution of ammonia in water
  • inert organic solvents such as ethyl acetate, dioxane or methanol
  • ammonia surrogates such as ammonium salts (for instance ammonium chloride).
  • compounds of the formula (IIIg-2), wherein R1, R3, R5, R10 and R11 are as described in formula (I), may be prepared by reacting compounds of the formula (IIIg-4), wherein R1, R3 and R5 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), with compounds of the formula HN(R11)C(O)OR10 (XL-c), wherein R10 and R11 are as defined for compounds of the formula (I), optionally in the presence of a catalyst, for example palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, optionally in form of a chloroform adduct), or a palladium pre-catalyst such as for
  • the anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid.
  • an acid such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like
  • an organic acid such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid.
  • a great number of such acids are known to a person skilled in the art.
  • Compounds of formula (IIIh-1), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), and X- is an anion, can be made from compounds of the formula (IIIh-2), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), by treatment with an acid, such as the acids listed above.
  • the reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents.
  • a solvent for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents.
  • the reaction can be done in a temperature range between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at ambient temperature.
  • the reaction can be done neat, or in a solvent, for instance an organic solvent, such as dioxane or acetic acid, or a mixture thereof.
  • the reaction can be performed in the presence or in the absence of a drying agent, such as for example in the presence of molecular sieves, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 80 °C.
  • a drying agent such as for example in the presence of molecular sieves
  • compounds of the formula (IIIf-3), wherein R1 and R4 are as defined for compounds of the formula (I), and in which R 5 is C1-C3alkyl or C3-C4cycloalkyl can be prepared by reacting compounds of the formula (IIIf-4), wherein R1 is as defined for compounds of the formula (I) and R5 is C1-C3alkyl or C3- C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, with hydrazine compounds of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 is as defined for compounds of the formula (I), under analogous conditions 109921
  • Compounds of the formula (IIIf-4), wherein R1 is as defined for compounds of the formula (I) and R5 is C1-C3alkyl or C3-C4cycloalkyl, and R L is -NH2 or -OC1-C4alkyl, can be prepared by reacting compounds of the formula (IIIf-5), wherein R1 is as defined for compounds of the formula (I), with compounds of the formula (IIIf-6) or a tautomer thereof, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R 5 is C1-C3alkyl or C3- C4cycloalkyl, and R L is -NH2 or -OC1-C4alkyl, in the presence of a coupling reagent, such as, for example, HATU (1-[bis(dimethylamino)-methylene]
  • Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N- dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N- dimethylformamide, in a temperature range of -100 to +300 °
  • Scheme 23 [0177] Alternatively, compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which R a is C1-C6alkyl or benzyl, can be prepared (Scheme 23) by cyclization of compounds of the formula (LI-1), wherein A, R 2a and R 2b are as described in formula (I), and in which R a is C1-C6alkyl or benzyl, under analogous conditions already described above in Scheme 17 (transformation LI into L, cyclization).
  • X4 is a leaving group, like, for example a halogen atom, preferably bromine, chlorine or iodine (even more preferably chlorine), or alternatively X 4 is a leaving group like a sulfonate, for example a triflate, or an alkylsulfonyl or arylsulfonyl group, like Me-SO2- or benzenesulfonyl, are known or even commercially available, or they can be made by known methods.
  • compounds of the formula (LII-2) are reacted with a :CF2 carbene species, generated from difluoromethylating agents such a difluoroacetate X c CF2COONa or a difluoromethyl(phosphonate) X c CF2P(O)(OEt)2 reagent, wherein X c can be chloro or bromo, in the presence of a base such as for example sodium or potassium carbonate, or sodium or potassium hydroxide, in an appropriate solvent like for example acetonitrile, ⁇ , ⁇ -dimethylformamide or N- methyl-2-pyrrolidone (NMP), optionally in a mixture with water, optionally in the presence of an additive (such as 2'-hydroxyacetophenone), and at temperature between -40°C to 80°C.
  • difluoromethylating agents such as a difluoroacetate X c CF2COONa or a difluoromethyl(phosphonate) X c
  • compounds of the formula (LII-2), wherein A and R2a are as described in formula (I), and in which R a is C1-C6alkyl or benzyl can be prepared by reacting compounds of the formula (LII-1), wherein A and R2a are as described in formula (I), and R2b is a halogen, preferably F, Cl, or Br (more preferably F), and in which Ra is C1-C6alkyl or benzyl, with 2-(methylsulfonyl)ethanol, in the presence of a base, such as sodium hydride, in an inert solvent, such as ⁇ , ⁇ -dimethylformamide or N-methyl-2-pyrrolidone (NMP), at temperatures between 0°C and 80°C, preferably around 0°C.
  • a base such as sodium hydride
  • an inert solvent such as ⁇ , ⁇ -dimethylformamide or N-methyl-2-pyrrolidone (NMP)
  • the in situ generated compound of the formula (LII-1), wherein R 2b is hydroxyl protected by 2-(methylsulfonyl)ethyl (via aromatic nucleophilic substitution), may be isolated.
  • acid deprotection conditions such as treating with aq. HCl under stirring, preferably under cooling conditions, to directly afford compounds of the formula (LII-2).
  • the reactants can be reacted in the presence of a base.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N- dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU).
  • DBU 1,8- diazabicyclo[5.4.0]undec-7-ene
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N- methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. [0187] The reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • an inorganic salt which forms, for example silver chloride is insoluble and thus precipitates from the reaction mixture.
  • the compounds of formula (I) which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this 109921
  • N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H2O2/urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride.
  • Tables A-1 to A-30 and Tables B-1 to B-5 can be prepared according to the methods described above.
  • the examples which follow are intended to illustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula (I- A) and (I-B).
  • Tables A-1 to A-30 (formula I-A) [0201]
  • Table A-1 provides 20 compounds A-1.001 to A-1.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z.
  • Table A-2 provides 20 compounds A-2.001 to A-2.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z.
  • Table A-3 provides 20 compounds A-3.001 to A-3.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Br, R1 is H and Q are as defined in table Z.
  • Table A-4 provides 20 compounds A-4.001 to A-4.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z.
  • Table A-5 provides 20 compounds A-5.001 to A-5.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z.
  • Table A-6 provides 20 compounds A-6.001 to A-6.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z.
  • Table A-7 provides 20 compounds A-7.001 to A-7.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z.
  • Table A-8 provides 20 compounds A-8.001 to A-8.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z.
  • Table A-9 provides 20 compounds A-9.001 to A-9.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table A-10 provides 20 compounds A-10.001 to A-10.020 of formula I-A wherein R2a is CH3, A is CH, R 2b is Cyp, R1 is CH3 and Q are as defined in table Z.
  • Table A-11 provides 20 compounds A-11.001 to A-11.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is Cl, R1 is H and Q are as defined in table Z.
  • Table A-12 provides 20 compounds A-12.001 to A-12.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is Cl, R1 is CH3 and Q are as defined in table Z.
  • Table A-13 provides 20 compounds A-13.001 to A-13.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is Br, R1 is H and Q are as defined in table Z.
  • Table A-14 provides 20 compounds A-14.001 to A-14.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is Br, R 1 is CH 3 and Q are as defined in table Z.
  • Table A-15 provides 20 compounds A-15.001 to A-15.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is CF3, R1 is H and Q are as defined in table Z.
  • Table A-16 provides 20 compounds A-16.001 to A-16.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is CF3, R1 is CH3 and Q are as defined in table Z.
  • Table A-17 provides 20 compounds A-17.001 to A-17.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is CHF2, R1 is H and Q are as defined in table Z.
  • Table A-18 provides 20 compounds A-18.001 to A-18.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is CHF2, R1 is CH3 and Q are as defined in table Z.
  • Table A-19 provides 20 compounds A-19.001 to A-19.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table A-20 provides 20 compounds A-20.001 to A-20.020 of formula I-A wherein R2a is CH2CH3, A is CH, R 2b is Cyp, R1 is CH3 and Q are as defined in table Z. 109921
  • Table A-21 provides 20 compounds A-21.001 to A-21.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is Cl, R1 is H and Q are as defined in table Z.
  • Table A-22 provides 20 compounds A-22.001 to A-22.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is Cl, R1 is CH3 and Q are as defined in table Z.
  • Table A-23 provides 20 compounds A-23.001 to A-23.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is Br, R1 is H and Q are as defined in table Z.
  • Table A-24 provides 20 compounds A-24.001 to A-24.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is Br, R1 is CH3 and Q are as defined in table Z.
  • Table A-25 provides 20 compounds A-25.001 to A-25.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is CF3, R1 is H and Q are as defined in table Z.
  • Table A-26 provides 20 compounds A-26.001 to A-26.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is CF3, R1 is CH3 and Q are as defined in table Z.
  • Table A-27 provides 20 compounds A-27.001 to A-27.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is CHF2, R1 is H and Q are as defined in table Z.
  • Table A-28 provides 20 compounds A-28.001 to A-28.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is CHF 2 , R 1 is CH 3 and Q are as defined in table Z.
  • Table A-29 provides 20 compounds A-29.001 to A-29.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is Cyp, R1 is H and Q are as defined in table Z.
  • Table A-30 provides 20 compounds A-30.001 to A-30.020 of formula I-A wherein R2a is Cyp, A is CH, R 2b is Cyp, R1 is CH3 and Q are as defined in table Z.
  • Table B-1 provides 19 compounds B-1.001 to B-1.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R 1 is H, R 5 is CH3 and R 4x are as defined in table Z1.
  • Table B-2 provides 19 compounds B-2.001 to B-2.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R 1 is H, R 5 is CH2CH3 and R 4x are as defined in table Z1.
  • Table B-3 provides 19 compounds B-3.001 to B-3.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R 1 is H, R 5 is cyclopropyl and R 4x are as defined in table Z1.
  • Table B-4 provides 19 compounds B-4.001 to B-4.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R 1 is H, R 5 is OCH3 and R 4x are as defined in table Z1.
  • Table B-5 provides 19 compounds B-5.001 to B-5.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R 1 is H, R 5 is Br and R 4x are as defined in table Z1.
  • Table Z1 Substituent definitions of R 4x 109921
  • Cyp represents cyclopropyl.
  • Also made available are certain intermediate compounds as shown in Schemes 1 to 20, some of which are novel.
  • a compound of formula IIa-1 as shown below, where A, R2a and R2b are as defined for compounds of formula (I); for instance, where A, R2a and R2b are as described in Tables A-1 to A-30 and Tables B-1 to B-5; in particular where A is CH, R2a is cyclopropyl, and R2b is chloro, bromo, difluoromethoxy, difluoromethyl, or trifluoromethyl, preferably difluoromethoxy, difluoromethyl, or trifluoromethyl;
  • ⁇ A compound of formula IIa-2 as shown below, where A, R2a and R2b are as defined for compounds of formula (I), and Ra is C1-C6alkyl or benzyl, preferably Ra is methyl or ethyl; for instance, where A, R2a and R2b are as described in Tables A-1 to A-30 and Tables B-1 to B-5, in particular where A is CH, R2a is cyclopropy
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate.
  • Examples of the above mentioned animal pests are: ⁇ from the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivor
  • ⁇ from the order Anoplura for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.
  • ⁇ from the order Coleoptera for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna s
  • ⁇ from the order Hemiptera for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocor
  • Thyanta spp Triatoma spp., Vatiga illudens, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysom
  • Vespa spp. from the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminata; 109921
  • ⁇ from the order Orthoptera for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp., and Schistocerca spp.
  • ⁇ from the order Psocoptera for example, Liposcelis spp.
  • Siphonaptera for example, Ceratophyllus spp., Ctenocephalides spp.
  • Thysanoptera for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; ⁇ from the order Thysanura, for example, Lepisma saccharina.
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Bel
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H.
  • the active ingredients according to the invention can be used for controlling, i.e.
  • pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coco-nut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and
  • compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
  • the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia 109921
  • Coreopsis spp. Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I.
  • Iresines spp. Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp.
  • the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A.
  • Daucus carota Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the compounds of formula (I) are particularly suitable for control of ⁇ a pest of the order Hemiptera, for example, one or more of the species Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in vegetables, soybeans, and sugarcane); 109921
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vip e.g. Vip1, Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1FA 2 , Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • 83192 FF acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1FA 2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety
  • transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2 . Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St.
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained f rom Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. [0260] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Bioschreib und Nachhaltmaschine, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0392225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818 and EP-A-0353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
  • Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related proteins" (PRPs; see e.g. EP-A-0392225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1, KP4 or KP6 toxins stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related
  • compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and 109921
  • the present invention provides a compound of the first aspect for use in therapy.
  • the present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal.
  • the present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal.
  • the present invention further provides a compound of the first aspect, for use in preventing and/or treating diseases transmitted by ectoparasites.
  • the present invention provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling parasites in or on an animal.
  • the present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal.
  • the present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and/or treating diseases transmitted by ectoparasites.
  • the present invention provides the use of a compound of the first aspect, in controlling parasites in or on an animal.
  • the present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal.
  • controlling when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and/or preventing further pest or parasite infestation.
  • treating when used in context of parasites in or on an animal refers to restraining, slowing, stopping or reversing the progression or severity of an existing symptom or disease.
  • preventing when used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal.
  • animal when used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal.
  • Non-human mammals include, but are not limited to, livestock animals and companion animals.
  • Livestock animals include, but are not limited to, cattle, camelids, pigs, sheep, goats and horses.
  • Companion animals include, but are not limited to, dogs, cats and rabbits.
  • a "parasite” is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense.
  • An "endoparasite” is a parasite which lives in the host animal.
  • Ectoparasite is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice).
  • the Acari (or Acarina) sub-class comprises ticks and mites.
  • Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros.
  • Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates.
  • Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and 109921
  • Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis.
  • Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes.
  • Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola ovis and Bovicola bovis.
  • the term "effective amount" when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal.
  • the effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
  • the compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally ' and subcutaneously. Topical administration is preferred.
  • Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip.
  • the compounds of the invention may be administered by means of an ear tag or collar.
  • Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts.
  • Pharmaceutically and veterinary acceptable salts and common methodology for preparing them are well known in the art. See, for example, Gould, P.L., "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201 -217 (1986); Bastin, R.J., et al.
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method 109921
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005/113886 or WO 2007/090739.
  • Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g.
  • Ataenius spp. e.g. Black turfgrass ataenius, A. spretulus
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls (Margarodes spp.)
  • mole crickets tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Examples of such parasites are: ⁇ Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Chrysomyia spppp
  • Siphonapta for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. ⁇
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. ⁇
  • Blattarida for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., 109921
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spp., Tryptodendron spp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spp., and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • a compound TX controls one or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • a compound TX controls one or more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp.
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.
  • a compound TX controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis 109921
  • a compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops.
  • a compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P is suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
  • advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
  • certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera.
  • Israelensis + TX Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thurin-giensis subsp. Tenebrionis + TX, Bacillus thuringiensis subspec.
  • lecontei NPV + TX nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca- 2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp.
  • TX trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc-call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp.
  • acridum + TX Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020/193387) + TX, methyl (
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, 109921
  • amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP ®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • TX Lagenidium giganteum (Laginex®) + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii (Mycotal®) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metarhizium anisopliae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX
  • TX Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta/ChemChina); + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, P
  • TX Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp.
  • Rhizobia Distal®, Vault®
  • Rhizoctonia + TX Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp.
  • Trichoderma asperellum T34 Biocontrol®
  • TX Trichoderma atroviride
  • Trichoderma gamsii Tenet® + TX, 109921
  • Trichoderma harzianum rifai Mycostar®
  • TX Trichoderma harzianum T-22
  • Trianum-P® PlantShield HC®, RootShield®, Trianum-G® + TX
  • LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp.
  • TX maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.
  • TX Bombus terrestris (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®, Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp.
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus,
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho- Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) +
  • NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX
  • Bacillus pumilus in particular strain BU F-33, having NRRL Accession No.50185 (CARTISSA® from BASF, EPA Reg. No. 71840-19) + TX
  • Bacillus subtilis CX-9060 from Certis USA LLC
  • Bacillus sp. in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S.
  • Patent No.7,094,592 + TX Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661 and described in U.S.
  • Patent No.6,060,051 available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US
  • TX Paenibacillus polymyxa
  • strain AC-1 e.g. TOPSEED® from Green Biotech Company Ltd.
  • TX Paenibacillus 109921
  • NRRL B-21856 (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX, Saccharomyces cerevisiae, in particular strains CNCM No.1-3936, CNCM No.1-3937, CNCM No.1-3938 or CNCM No.1-3939 (WO 2010/086790) from
  • DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX
  • Bacillus amyloliquefaciens in particular strain D747 (available as Double NickelTM from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No.7,094,592) + TX
  • Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX
  • Bacillus licheniformis in particular strain SB3086, having Accession No.
  • ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAFTM from Novozymes) + TX, Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX, Bacillus mycoides, isolate, having Accession No. B-30890 (available as BMJ TGAI® or WG and LifeGardTM from Certis USA LLC) + TX, Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX, Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No.
  • Patent No.5,061,495 + TX Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No.
  • DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX, Paenibacillus polymyxa ssp. plantarum (WO 2016/020371) from BASF SE + TX, Paenibacillus sp. strain having Accession No.
  • NRRL B-50972 or 109921 83192 FF Accession No. NRRL B-67129, WO 2016/154297 + TX, Pseudomonas chlororaphis strain AFS009, having Accession No. NRRL B-50897, WO 2017/019448 (e.g., HOWLERTM and ZIO® from AgBiome Innovations, US) + TX, Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert) + TX, Pseudomonas fluorescens strain A506 (e.g.
  • BIOKUPRUMTM by AgriLife + TX
  • Chaetomium globosum available as RIVADIOM® by Rivale
  • TX Cladosporium cladosporioides
  • strain H39 having Accession No. CBS122244, US 2010/0291039 (by Stichting Moowgrass Onderzoek) + TX
  • Coniothyrium minitans in particular strain CON/M/91-8 (Accession No. DSM9660, e.g.
  • strain ICC 080 having Accession No. IMI 392151 (e.g., BIO-TAMTM from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM 109921
  • T-Gro from Andermatt Biocontrol + TX
  • Trichoderma atroviride strain 77B T77 from Andermatt Biocontrol
  • Trichoderma atroviride strain ATCC 20476 IMI 206040
  • Trichoderma atroviride strain LC52 e.g. Tenet by Agrimm Technologies Limited
  • Trichoderma atroviride strain LU132 e.g. Sentinel from Agrimm Technologies Limited
  • TX Trichoderma atroviride strain NMI no. V08/002388 + TX
  • Trichoderma atroviride strain NMI no. V08/002389 + TX Trichoderma atroviride strain NMI no.
  • Patent No.8,431,120 (from Bi- PA)) + TX, Trichoderma atroviride,strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A.
  • Trichoderma gamsii strain ICC080 IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.
  • + TX Trichoderma harmatum + TX
  • Trichoderma harmatum having Accession No. ATCC 28012 + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g.
  • Trichodex® from Makhteshim, US + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro), + TX, Trichoderma harzianum strain DB 103 (available as T- GRO® 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g. Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g.
  • Trichoderma polysporum strain IMI 206039 e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden
  • TX Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX
  • Trichoderma virens also known as Gliocladium virens
  • strain GL-21 e.g. SoilGard by Certis, US
  • Trichoderma virens strain G- 41 formerly known as Gliocladium virens (Accession No.
  • ATCC 20906 (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1(e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No.
  • NM 99/06216 e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.
  • TX Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No.
  • WCS850 deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; 109921
  • NRRL B-5015 + TX
  • Bacillus amyloliquefaciens in particular strain FZB42 e.g. RHIZOVITAL® from ABiTEP, DE
  • Bacillus amyloliquefaciens in particular strain IN937a + TX Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection) + TX
  • Bacillus amyloliquefaciens SB3281 ATCC # PTA-7542, WO 2017/205258
  • Bacillus amyloliquefaciens TJ1000 available as QUIKROOTS® from Novozymes
  • Bacillus cereus family member EE128 NRRL No.
  • YIELD SHIELD® from Bayer Crop Science, DE
  • + TX Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B-50421 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g.
  • BIOBOOST® from Brett Young Seeds + TX, Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g.
  • PRORADIX® from Sourcon Padena + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708), + TX, Sinorhizobium meliloti strain NRG- 185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g.
  • M yrothecium verrucaria strain AARC-0255 e.g. DiTeraTM from Valent Biosciences
  • Penicillium bilaii strain ATCC 22348 e.g. JumpStart® from Acceleron BioAg
  • Penicillium bilaii strain ATCC ATCC20851 TX
  • Purpureocillium lilacinum previously known as Paecilomyces lilacinus
  • Trichoderma atroviride strain SC1 (described in WO2009/116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g.
  • aizawai in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp.
  • serotype H-7 e.g. FLORBAC® WG from Valent BioSciences, US
  • TX Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX
  • israeltaki strain ABTS 351 + TX Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. DIPEL® ES from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp.
  • BMP 123 from Becker Microbial Products, IL, BARITONE from Bayer CropScience
  • TX Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX
  • israeltaki strain PB 54 + TX Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX, Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var.
  • SD-5428 e.g. NOVODOR® FC from BioFa DE
  • Bacillus thuringiensis var. Colmeri e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory
  • MBI206 TGAI and ZELTO® from Marrone Bio Innovations + TX
  • Chromobacterium subtsugae in particular strain PRAA4-1T e.g. MBI- 109921
  • TX Chromobacterium subtsugae in particular strain PRAA4-1T
  • 83192 FF 203 e.g. GRANDEVO® from Marrone Bio Innovations
  • TX Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX
  • Paenibacillus popilliae (formerly Bacillus popilliae, e.g. MILKY SPORE POWDERTM or MILKY SPORE GRANULARTM from St. Gabriel Laboratories) + TX
  • Serratia entomophila e.g.
  • ATCC74250 e.g. BOTANIGUARD® ES and MYCONTROL- O® from Laverlam International Corporation
  • TX Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017/066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX, Zoophtora radicans + TX; Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armiger
  • Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, LactoBacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp. in particular Rhizobium trifolii + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp.
  • the designation is not a "common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name”, a “traditional name”, a “compound name” or a “development code” is used or, if neither one of those designations nor a "common name” is used, an "alternative name” is employed.
  • "CAS Reg. No” means the Chemical Abstracts Registry Number.
  • the active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2
  • the compounds and mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a compound or mixture respectively as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.
  • the mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture com-posed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequen-tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention.
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface- active substances or combinations thereof. 109921
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethyl-formamide, dimethyl sulfoxide, 1,4-dioxane, diprop
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, 109921
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formula-tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates: ⁇ active ingredient: 1 to 95 %, preferably 60 to 90 % ⁇ surface-active agent: 1 to 30 %, preferably 5 to 20 % ⁇ liquid carrier: 1 to 80 %, preferably 1 to 35 % 109921
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • the mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity.
  • Suitable additions to active ingredients are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, 109921
  • stabilizers for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, 109921
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredi-ent can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application).
  • systemic action systemic action
  • the active ingredient in solid form into the locus of the plants for example into the soil, for example in the form of granules (soil application).
  • paddy rice crops such granules can be metered into the flooded paddy-field.
  • the compounds of formula (I) of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula (I).
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • the compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m 2 .
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a ) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - 20 % [0335] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % [0336] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Coated granules Active ingredients 8 % polyethylene glycol (mol. wt.200) 3 % Kaolin 89 % [0339] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 % [0340]
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 109921
  • 83192 FF 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water)
  • 83192 FF 1,2-benzisothiazolin-3-one in the form of a 20% solution in water
  • 83192 FF 1,2-benzisothiazolin-3-one in the form of a 20% solution in water
  • 83192 FF 1,2-benzisothiazolin-3-one in the form of a 20% solution in water
  • 83192 FF 1,2-benzisothiazolin-3-one in the form of a 20% solution in water
  • 83192 FF 1,2-benzisothiazolin-3-one in the form of a 20% solution in water
  • Silicone oil in the form
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Free radicals represent methyl groups.1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds.
  • the characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion [M+H] + or [M-H]-.
  • Method 1 [0344] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • Method 3 [0346] Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector.
  • an electrospray source Polarity: Positive and Negative Polarity Switch
  • Method 4 [0347] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • SQD SQDII or QDA Single quadrupole mass spectrometer
  • Capillary 0.8-3.00 kV
  • Cone 5-30 V
  • Source Temperature 120-150°C
  • Desolvation Temperature 350- 600°C
  • Cone Gas Flow 50-150
  • Step 2 Preparation of [2-(cyclopropylamino)-4-(trifluoromethyl)phenyl]ammonium;chloride (I-2) (I-2) [0350]
  • N-cyclopropyl-2-nitro-5-(trifluoromethyl)aniline (synthesis described hereabove) (2.0 g, 8.1 mmol) in ethyl acetate (20 mL) was added 10% palladium on carbon (0.17 g) under nitrogen atmosphere.
  • the reaction mixture was stirred under hydrogen balloon atmosphere at room temperature for 8 hours. Reaction 109921
  • Step 3 Preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-benzimidazol-2-one (I-3) [0352] To a suspension of [2-(cyclopropylamino)-4-(trifluoromethyl)phenyl]ammonium;chloride (preparation described above) (1.0 g, 3.6 mmol, 90 mass%) in ethyl acetate (30 mL) was added N,N-diethylethanamine (1.9 g, 18 mmol) at 0°C, followed by bis(trichloromethyl) carbonate (0.54 g, 1.8 mmol) and the reaction mixture was stirred at room temperature for 16 hours.
  • Step 4 Preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-benzimidazol-2-one (I-4) (I-4) [0354] To a solution of 3-cyclopropyl-5-(trifluoromethyl)-1H-benzimidazol-2-one (preparation described above) (1.5 g, 6.2 mmol) in acetonitrile (15 mL) was added N-chloro succinimide (4.4 g, 25 mmol) at room temperature. The reaction mixture was stirred at room temperature for 27 hours, after what it was poured into sodium meta bisulfate solution (30 mL).
  • Step 6 Preparation of 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) [0358] To a solution of methyl 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylate (preparation described above) (2.0 g, 2.3 mmol, 35 mass%) in methanol (20 mL) and water (10 mL) was added lithium hydroxide (0.28 g, 12 mmol) at room temperature. The reaction mixture was stirred at room temperature for 3 hours, then concentrated and the residue was acidified with 2N HCl and extracted with ethyl acetate.
  • Example E2 Preparation of N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl- 6-(difluoromethoxy)-2-oxo)-3H-benzimidazole-4-carboxamide (P30) [0362] To a mixture of 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I-12) (51.2 mg, 0.18 mmol, 1 equiv.) and [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2648588-51-4, prepared as described in WO 21/105091) (0.198 mmol, 1.1 equiv.) in DMA (0.75 mL)
  • N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-2-oxo- 6-(trifluoromethyl))-3H-benzimidazole-4-carboxamide (compound P11) was prepared from 1-cyclopropyl-2- oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) and [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5- methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-24, prepared as described below) by following above protocol in analogy.
  • Example E4 Preparation of N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-N- methyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxamide (P57) [0371] To a mixture of 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) (101 mg, 0.353 mmol, 1 equiv.) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-methyl- ammonium chloride (CAS 3024825-36-0, prepared as described in WO 23/247360) (105 mg, 0.424 mmol, 1.2 equiv.)
  • Step 2 Preparation of methyl 3-(cyclopropylamino)-5-hydroxy-2-nitro-benzoate (I-8) [0375] To a solution of methyl 3-(cyclopropylamino)-5-fluoro-2-nitro-benzoate (I-7) (preparation described hereabove) (8.0 g, 31.0 mmol) in anhydrous N,N-dimethylformamide (160 mL) under inert atmosphere was added 2-(methylsulfonyl)ethanol (5.8 g, 47 mmol). The solution was cooled to 0°C and sodium hydride (60% suspension in paraffin oil, 3.7 g, 93 mmol) was added portionwise over 20 minutes.
  • 2-(methylsulfonyl)ethanol 2-(methylsulfonyl)ethanol
  • Step 3 Preparation of methyl 3-(cyclopropylamino)-5-(difluoromethoxy)-2-nitro-benzoate (I-9) [0377] To a solution of methyl 3-(cyclopropylamino)-5-hydroxy-2-nitro-benzoate (I-8) (preparation described hereabove) (5.6 g, 22.2 mmol) in N,N-dimethylformamide (40 mL) were added sodium chlorodifluoroacetate (3.72 g, 24.4 mmol), sodium carbonate (2.87 g, 26.6 mmol) and water (0.57 mL). The reaction mixture was stirred at 80°C for 3 hours, then cooled to room temperature.
  • Step 4 Preparation of methyl 2-amino-3-(cyclopropylamino)-5-(difluoromethoxy)benzoate (I-10) [0379] A solution of methyl 3-(cyclopropylamino)-5-(difluoromethoxy)-2-nitro-benzoate (I-9) (preparation described hereabove) (2.0 g, 6.62 mmol) in methanol (130 mL) was flushed with argon for 5 minutes. Palladium on charcoal (10%) (300 mg) was added, the suspension sparged with hydrogen and the mixture stirred at 23°C for 100 minutes under a slight overpressure of hydrogen (balloon).
  • Step 5 Preparation of methyl 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylate (I-11) [0381] To a solution of methyl 2-amino-3-(cyclopropylamino)-5-(difluoromethoxy)benzoate (I-10) (preparation described hereabove) (1.8 g, 6.61 mmol) in anhydrous tetrahydrofuran (35 mL) at 0°C under inert atmosphere was added triphosgene (bis(trichloromethyl)carbonate; 1.962 g, 6.61 mmol), followed by N,N- diisopropylethylamine (3.43 mL, 19.84 mmol) dropwise over five minutes.
  • triphosgene bis(trichloromethyl)carbonate
  • Step 6 Preparation of 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I-12) (I-12) [0383] To a suspension of methyl 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylate (I-11) (preparation described hereabove) (1.9 g, 6.37 mmol) in tetrahydrofuran (25 mL) were added water (12 mL) and lithium hydroxide monohydrate (324 mg, 7.64 mmol).
  • Example PI-2 Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 23)
  • Step 1 Preparation of (5-bromopyrimidin-2-yl)hydrazine (I-16)
  • 5-bromo-2-chloro-pyrimidine 15.0 g, 77.55 mmol
  • methanol 150 mL
  • hydrazine hydrate 10.1 mL, 155.1 mmol, 2.0 equiv.
  • Step 2 Preparation of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17) [0387] tert-Butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (CAS 85642-13-3) (70.0 g, 353 mmol, 1 equiv.) was mixed with 2-methyltetrahydrofuran (1.12 L) and N,N-dimethylformamide-dimethylacetal (DMF- DMA, 70 mL, 530 mmol, 1.5 equiv.), and the mixture heated to 40°C for 2 hours.
  • DMF- DMA N,N-dimethylformamide-dimethylacetal
  • tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) was prepared from tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (CAS 85642-13-3) and N,N-dimethylacetamide-dimethyl acetal (CAS 18871-66-4) by following above protocol in analogy.
  • Step 3 Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-19) [0391] To a mixture of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17, prepared as described above) (7.73 g, 30.5 mmol, 1.2 equiv.) in 1,4-dioxane (32 mL) were added (5-bromopyrimidin-2-yl)hydrazine (I-16) (5.0 g, 25.4 mmol, 1.0 equiv.) and acetic acid (32 mL).
  • tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-20) was prepared from tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) and (5-bromopyrimidin-2-yl)hydrazine (I-16) by applying above protocol in analogy.
  • tert-butyl N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-21) was prepared from tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) and (5-fluoropyrimidin-2-yl)hydrazine (CAS 104408-28-8) by applying above protocol in analogy.
  • tert-butyl N-[(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-22) was prepared from tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) and (5-chloropyrimidin-2-yl)hydrazine (CAS 823-90-5) by applying above protocol in analogy.
  • Example PI-3 Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-31)
  • Step 1 Preparation of tert-butyl N-[(1S)-2-[[amino(cyclopropyl)methylene]amino]-1-methyl-2-oxo- ethyl]carbamate (I-27)
  • (2S)-2-(tert-butoxycarbonylamino)propanoic acid 5.00 g, 26.4 mmol, 1.0 equiv.
  • cyclopropanecarboximidoylammonium chloride 5.74 g, 47.6 mmol, 1.8 equiv.
  • tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-ethyl]carbamate (I-28) was prepared from (2S)-2-(tert-butoxycarbonylamino)propanoic acid and propanimidoyl-ammonium chloride by applying above protocol in analogy.
  • TLC 50% EtOAc in cyclohexane
  • Step 2 Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-29) [0409] To above solution in N,N-dimethylformamide of tert-butyl N-[(1S)-2- [[amino(cyclopropyl)methylene]amino]-1-methyl-2-oxo-ethyl]carbamate (I-27) were added (5-bromopyrimidin- 2-yl)hydrazine (I-16, prepared as described above) (7.99 g, 1.6 equiv.) and acetic acid (16.70 g, 10.0 equiv.).
  • reaction mixture was heated at 45°C for 90 minutes, then at 60°C for 1 hour. After cooling to room temperature, the mixture was diluted with a saturated aqueous solution of sodium carbonate, and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure.
  • tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I- 30) was prepared from tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-ethyl]carbamate (I-28) and (5-bromopyrimidin-2-yl)hydrazine (I-16) by applying above protocol in analogy.
  • Step 2 Preparation of (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethanamine (I-34) (I-34) [0419] To a solution of 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethyl]isoindoline- 1,3-dione (I-33) (3.0 g, 6.29 mmol) in ethanol (60 mL) was added hydrazine hydrate (0.794 g, 15.7 mmol, 2.5 equiv.) dropwise.
  • Example PI-5 Preparation of [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38) (I-38) Step 1: Preparation of ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1-yl]thiazole-5- carboxylate (I-35) [0421] Ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1-yl]thiazole-5-carboxylate (I-35) was prepared from tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-e
  • Step 3 Preparation of tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I- 37) (I-37) [0425] To a solution of tert-butyl N-[1-[2-(5-carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-36) (4.0 g, 10.9 mmol) in acetonitrile (40 mL) at 20°C was added triethylamine (4.7 mL, 33.6 mmol).
  • Step 4 Preparation of [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 38) [0427] [(1S)-1-[2-(5-Cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38) was prepared from tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-37) by applying above protocol ‘Example PI-3, step 3’ in analogy.
  • tert-butyl N-[(1S)-1-[2-(5-chloropyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-41) was prepared from tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate and 2-chloro-5-hydrazinylpyrazine (prepared as described in WO 2021/126923) by applying above protocol in analogy.
  • LCMS (method 3): retention time 1.09 min, m/z 325/327 [M+H] + .
  • Step 2 Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium;2,2,2- trifluoroacetate (I-14) 109921
  • Example PI-7 Preparation of 1-cyclopropyl-6-(difluoromethyl)-2-oxo-3H-benzimidazole-4-carbonyl fluoride (I- 39)
  • Step 1 Preparation of methyl 3-(cyclopropylamino)-2-nitro-benzoate
  • a solution of methyl 3-fluoro-2-nitro-benzoate (CAS 1214353-57-7) (5.00 g) in acetonitrile (125 mL) were added cyclopropyl amine (1.93 mL) and potassium carbonate (6.95 g). The suspension was stirred at 60°C for 20 hours.
  • Step 2 Preparation of methyl 2-amino-3-(cyclopropylamino)benzoate [0436] To a solution of methyl 3-(cyclopropylamino)-2-nitro-benzoate (preparation described hereabove) (28.4 g) in methanol (360 mL) were added zinc powder (54.9 g), followed by acetic acid (34.7 mL). The mixture was stirred at 35-60°C for 1 hour and 20 minutes. The mixture was then cooled, diluted with ethyl acetate (200 109921
  • the filtrate was made alkaline by adding an aqueous solution of sodium hydroxide and the product extracted with ethyl acetate (600 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo.
  • Step 3 Preparation of methyl 1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylate [0438] To a solution of methyl 2-amino-3-(cyclopropylamino)benzoate (preparation described hereabove) (6.3 g) in tetrahydrofuran (150 mL) at 0°C was added triphosgene (9.05 g). After 10 minutes, N,N- diisopropylethylamine (15.8 mL) was added and the reaction mixture was stirred at room temperature for 18 hours. After quenching with water (150 mL), the mixture was extracted with ethyl acetate.
  • Step 4 Preparation of methyl 6-bromo-1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylate [0440] To a solution of methyl 1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylate (preparation described hereabove) (4.5 g) in acetic acid (97 mL) at 23°C was added bromine (3.4 g). After stirring for 3.6 hours, another portion of bromine (3.4 g) was added, and stirring was continued for another 3.25 hours. The reaction mixture was quenched with water (200 mL), then with an aqueous solution of sodium thiosulfate until all bromine was consumed.
  • Step 5 Preparation of 6-bromo-1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylic acid
  • methanol 190 mL
  • lithium hydroxide monohydrate 2.42 g
  • the mixture was heated to 45°C and stirred for 15 hours. The volatiles were removed under reduced pressure and the residue was treated with 1M aqueous sodium hydroxide (150 mL), then washed with TBME (500 mL).
  • Step 6 Preparation of 1-cyclopropyl-2-oxo-6-vinyl-3H-benzimidazole-4-carboxylic acid
  • 6-bromo-1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylic acid (preparation described hereabove) (2.5 g) in ethanol (60 mL) and water (25 mL) under argon was added potassium vinyltrifluoroborate (1.69 g).
  • Step 7 Preparation of 1-cyclopropyl-6-formyl-2-oxo-3H-benzimidazole-4-carboxylic acid 109921
  • Step 8 Preparation of 1-cyclopropyl-6-(difluoromethyl)-2-oxo-3H-benzimidazole-4-carbonyl fluoride (I-39) (I-39) [0448] A suspension of crude 1-cyclopropyl-6-formyl-2-oxo-3H-benzimidazole-4-carboxylic acid (preparation described hereabove) (0.45 g) in dichloromethane (9 mL) was stirred in an ice bath. N-ethyl-N- (trifluoro- ⁇ 4-sulfanyl)ethanamine (DAST) (2.54 ml, 10 equiv.) was added neat over 1.5 minute.
  • DAST N-ethyl-N- (trifluoro- ⁇ 4-sulfanyl)ethanamine
  • Example PI-8 Preparation of [(1S)-1-[2-(5-carbamoylpyrazin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-40) 109921
  • Compound (I-40) was prepared by following in analogy the synthesis route for [(1S)-1-[2-(5- carbamoylpyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 3024825-20-2) outlined in WO 23/247360 (Example PI-4 on page 147), but replacing N,N-dimethylformamide dimethyl acetal with N,N- dimethylacetamide-dimethyl acetal (CAS 18871-66-4) in step 1.
  • Example PI-9 Preparation of [(1S)-1-[2-(5-chloropyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 42) (I-42) [0452] To a solution of tert-butyl N-[(1S)-1-[2-(5-chloropyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-41) (preparation described hereabove) (1 g) in 1,4-dioxane (8 mL) was added a 4.0 M solution of HCl in 1,4- dioxane (8.2 mL) at RT.
  • Example B1 Activity against Chilo suppressalis (Striped rice stemborer) [0456] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well).
  • the samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation.
  • Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
  • Example B2 Activity against Diabrotica balteata (Corn root worm) [0458] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
  • Example B3 Activity against Euschistus heros (Neotropical Brown Stink Bug) 109921
  • Feeding/Contact activity Bean leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 4 days after infestation. [0463] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P2, P6, P7, P10, P13, P16, P19, P21, P24, P25, P27, P32, P34, P38, P39, P41, P44, P48, P49.
  • Example B5 Activity against Myzus persicae (Green peach aphid).
  • Test compounds prepared from 10'000 ppm DMSO stock solutions were applied by pipette into 24- well microtiter plates and mixed with a nutrient solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.
  • Feeding/Contact activity Eggplant leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation. [0467] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P2, P16, P20, P21, P41, P51, P57.
  • Example B7 Activity against Plutella xylostella (Diamond back moth) [0468] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.
  • Example B8 Activity against Spodoptera littoralis (Egyptian cotton leaf worm) [0470] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
  • Example B9 Comparison of the insecticidal activity of compounds P2, P16 and P38 according to the invention with a structurally most closely comparable compound from the state of the art: [0472] Activity of compounds P2, P16 and P38 according to the preparatory examples and of a compound from WO 19/197468 against Spodoptera littoralis (Example B8 above), Chilo suppressalis (Example B1 above), Diabrotica balteata (Example B2 above), Plutella xylostella (Example B7 above) and Euschistus heros (Example B3 above) is summarized in Table B9.
  • Example B10 Comparison of the insecticidal activity of compound P16 according to the invention with structurally most closely comparable compounds from the state of the art: [0474] Activity of compound P16 according to the preparatory examples and of compounds from WO 20/094363 against Spodoptera littoralis (Example B8 above), Plutella xylostella (Example B7 above) and Euschistus heros (Example B3 above) is summarized in Table B10.
  • Example B11 Comparison of the insecticidal activity of compound P49 according to the invention with a structurally most closely comparable compound from the state of the art: [0476] Activity of compound P49 according to the preparatory examples and of a compound from WO 21/069575 against Spodoptera littoralis (Example B8 above), Diabrotica balteata (Example B2 above) and Euschistus heros (Example B3 above) is summarized in Table B11.

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Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

Description

109921 | 83192 FF PESTICIDALLY ACTIVE 2-OXOBENZIMIDAZOLE COMPOUNDS TECHNICAL FIELD [0001] The present invention relates to pesticidally active 2-oxobenzimidazole compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active 2-oxobenzimidazole compounds. The invention also relates to the preparation of these 2-oxobenzimidazole compounds, to intermediates useful in the preparation of these 2-oxobenzimidazole compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these 2-oxobenzimidazole compounds, to preparation of these compositions and to the use of these 2-oxobenzimidazole compounds or compositions in agriculture or horticulture, for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina. BACKGROUND WO 2023/037249, WO 2023/285175 and WO 2019/197468 describe certain fused heterobicyclic carboxamide derivatives with pesticidal activity. WO 2021/069567, WO 2021/069575, WO 2019/201835, and WO 2019/197468 describe some heteroaryI-triazole and heteroaryI- pyrazine compounds as pesticides. WO 2025/045835, WO 2025/045837 and WO 2025/045838 also disclose heteroaryI-triazole and heteroaryI- pyrazine compounds as pesticides. BRIEF SUMMARY [0003] It has now surprisingly been found that certain novel 2-oxobenzimidazole compounds have pesticidal activity. More specifically, certain novel 2-oxo-3H-benzimidazole-4-carboxamide compounds and aza analogues thereof, have pesticidal activity. [0004] Hence, the present invention accordingly relates, in a first aspect, to a compound of the formula (I) wherein A is CH or N; X is oxygen or sulfur; the staggered line represents the connection of Q to the rest of compound of the formula (I); 109921 | 83192 FF R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a is hydrogen, C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3- C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, cyano, C1-C3alkyl, and C1-C3haloalkyl; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4 is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo- pyridazinyl optionally N-substituted with a single substituent R4c; R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10 ; R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of the compound of formula (I). [0005] The present invention also provides a method of preparation of compounds of formula (I) as well as intermediate compounds useful in the preparation of compounds of formula (I). [0006] In a second aspect, the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient. [0007] In a third aspect, the present invention makes available a method of combating and controlling pests, such as insects, acarines, nematodes, or molluscs, which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to be attacked by a pest a pesticidally, such as insecticidally, acaricidally, nematicidally, or molluscicidally, effective amount of a compound as defined in the first aspect or of a composition as defined in the second aspect. [0008] In a fourth aspect, the present invention makes available a method for the protection of plant propagation material from the attack by a pest, such as insects, acarines, nematodes, or molluscs, which 109921 | 83192 FF comprises treating the propagation material or the site where the propagation material is planted, with an effective amount of a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect. [0009] In a fifth aspect, the present invention makes available a plant propagation material, such as a seed, comprising, or treated with, or coated with, or adhered thereto, a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect. [0010] The present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method for preventing and/or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula (I) as defined in the first aspect, to an animal in need thereof. DETAILED DESCRIPTION [0011] Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1- C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor-pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. [0012] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form. [0013] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. [0014] The compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation. [0015] The term "C1-Cnalkyl" as used herein refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- 109921 | 83192 FF methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl. [0016] The term "C1-Cnhaloalkyl" as used herein refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2- iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro- 2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3- difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3- trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3- pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2- fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4- bromobutyl or nonafluorobutyl. Accordingly "C1-C2fluoroalkyl" refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. [0017] The term "C1-Cnalkoxy" as used herein refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy. The term "haloC1-Cnalkoxy" as used herein refers to a C1-Cnalkoxy radical where one or more hydrogen atoms on the alkyl radical is replaced by the same or different halo atom(s) - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy. [0018] The term "C1-Cncyanoalkyl" as used herein refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1- (cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like. [0019] The term "C3-Cncycloalkyl" as used herein refers to a saturated monocyclic hydrocarbon radical attached via any of the ring carbon atoms and having 3 to n carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. [0020] The term "cyanoC3-Cncycloalkyl" as used herein refers to a C3-Cncycloalkyl where one of the hydrogen atoms in these radicals is replaced by a cyano group. [0021] The term "C3-Cncycloalkylcarbonyl" as used herein refers to a C3-Cncycloalkyl radical bonded to a carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule. Similarly the terms "C1- Cnalkylcarbonyl", "C1-Cnalkoxycarbonyl", "phenyloxycarbonyl" and "benzyloxycarbonyl" as used herein refers to an C1-Cnalkyl, C1-Cnalkoxy, phenyloxy and benzyloxy group bonded to a carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule. [0022] The term "C3-C4cycloalkylC1-C2alkyl" as used herein refers to a cyclopropyl or cyclobutyl radical bonded via a methylene or ethylene bridge to the rest of the molecule. When the C3-C4cycloalkylC1-C2alkyl 109921 | 83192 FF radical is substituted, the substituent(s) can be bonded to the C3-C4cycloalkyl radical and/or to the C1-C2alkyl bridge. [0023] The term "C1-Cnalkylsulfanyl" as used herein refers to a C1-Cnalkyl moiety linked through a sulfur atom. Similarly, the term "C1-Cnhaloalkylthio" or "C1-Cnhaloalkylsulfanyl" as used herein refers to a C1- Cnhaloalkyl moiety linked through a sulfur atom. Similarly, the term "C3-Cncycloalkylsulfanyl" refers to 3-n membered cycloalkyl moiety linked through a sulfur atom. [0024] The term "C1-Cnalkylsulfinyl" as used herein refers to a C1-Cnalkyl moiety linked through the sulfur atom of the S(=O) group. Similarly, the term "C1-Cnhaloalkylsulfinyl " or "C1-Cnhaloalkylsulfinyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O) group. Similarly, the term "C3- Cncycloalkylsulfinyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atom of the S(=O) group. [0025] The term "C1-Cnalkylsulfonyl" as used herein refers to a C1-Cnalkyl moiety linked through the sulfur atom of the S(=O)2 group. Similarly, the term "C1-Cnhaloalkylsulfonyl " or "C1-Cnhaloalkylsulfonyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O)2 group. Similarly, the term "C3-Cncycloalkylsulfonyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atom of the S(=O)2 group. [0026] The term "C2-Cnalkenyl" as used herein refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl. [0027] The term "C2-Cnalkynyl" as used herein refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl. [0028] Halogen or "halo" is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl. [0029] The term "optionally substituted" as used herein means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example, "C3-C4cycloalkyl is optionally substituted with 1 or 2 halogen atoms" means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halogen atom and C3-C4cycloalkyl substituted with 2 halogen atoms. [0030] As used herein, the term "controlling" refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced. [0031] As used herein, the term "pest" refers to insects and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest. [0032] As used herein, the term "effective amount" refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect. [0033] An effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to 109921 | 83192 FF be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances. [0034] As one of ordinary skill in the art will appreciate, compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in formula (I*) below: where A, R1, R2a, R2b, R3, Q and X are as defined in the first aspect. [0035] The present invention contemplates both racemates and individual enantiomers. Compounds of formula (I') having a preferred stereochemistry are set out below: [0036] Particularly preferred compounds of the present invention are compounds of formula (I’), where A, R1, R2a, R2b, R3, Q and X are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N- oxides of the compounds of formula (I’), and agrochemically acceptable salts thereof. [0037] Particularly preferred compounds of formula (I’) include compounds of formula (I’a) as shown below, where X is oxygen, and A, R1, R2a, R2b, R3 and Q are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I*a), and agrochemically acceptable salts thereof: [0038] Particularly preferred compounds of the present invention are compounds of formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a), where A is CH, X is oxygen, and where R1, R2a, R2b, R3, and Q are as defined in the first aspect, as shown with compounds of formula (I*b) and (I’b) below: 109921 | 83192 FF [0039] Embodiments according to the invention are provided as set out below. [0040] In an embodiment of each aspect of the invention, A is N. When A is N, the moiety containing A is a 2-oxo-imidazo[4,5-b]pyridine group. In another embodiment of each aspect of the invention, A is CH. In a preferred embodiment of each aspect of the invention, A is CH. When A is CH, the moiety containing A is a 2- oxo-benzimidazole group. [0041] In an embodiment of each aspect of the invention, X is oxygen (i.e. an oxygen atom). In an embodiment of each aspect of the invention, X is S (i.e. a sulfur atom). Preferably, in embodiments of each aspect of the invention, X is oxygen. [0042] In an embodiment of each aspect of the invention, R1 is as follows: A. R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B. R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl; or C. R1 is hydrogen, methyl, or cyclopropylmethyl; or D. R1 is hydrogen or methyl; or E. R1 is methyl; or F. R1 is hydrogen. [0043] In preferred embodiments of each aspects of the invention, R1 is hydrogen, methyl, or cyclopropylmethyl; or R1 is hydrogen or methyl. Most preferably, R1 is hydrogen. [0044] In an embodiment of each aspect of the invention, R2a is as follows: A. R2a is hydrogen, C1-C3alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; or B. R2a is hydrogen, C1-C3alkyl, C1-C3fluoroalkyl, cyclopropyl, cyclobutyl, or cyclopropyl substituted with a single fluoro or cyano; or C. R2a is C1-C3alkyl, C1-C3fluoroalkyl, cyclopropyl, or cyclopropyl substituted with a single fluoro or cyano; or D. R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; or E. R2a is methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; or F. R2a is methyl, ethyl, or cyclopropyl; or G. R2a is methyl or cyclopropyl; or H. R2a is cyclopropyl. 109921 | 83192 FF [0045] In preferred embodiments of each aspect of the invention, R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl. For instance, R2a is methyl, ethyl, or cyclopropyl. More preferably, R2a is cyclopropyl. [0046] In an embodiment of each aspect of the invention, R2b is as follows: A. R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3- C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, cyano, C1-C3alkyl, and C1-C3haloalkyl; or B. R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfonyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, cyclopropyl, or cyclopropyl substituted with one or two substituents independently selected from the group consisting of halogen, cyano, methyl, and trifluoromethyl; or C. R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl; or D. R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, or cyclopropyl; or E. R2b is halogen, C1-C3fluoroalkyl, C1-C3fluoroalkoxy, C1-C3fluoroalkylsulfonyl, or cyclopropyl; or F. R2b is halogen, C1-C3fluoroalkyl, C1-C3fluoroalkoxy, or cyclopropyl; or G. R2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; or H. R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl; or I. R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; or J. R2b is chloro, bromo, difluoromethyl, trifluoromethyl, or cyclopropyl; or K. R2b is chloro, difluoromethyl, or cyclopropyl; or L. R2b is trifluoromethyl; or M. R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, trifluoromethyl, or difluoromethoxy; or N. R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, or cyclopropyl; or O. R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, or cyclopropyl; or P. R2b is chloro, trifluoromethyl, difluoromethoxy, or cyclopropyl; or Q. R2b is trifluoromethyl or difluoromethoxy; or R. R2b is difluoromethyl, trifluoromethyl, or difluoromethoxy. [0047] In preferred embodiments of each aspect of the invention, R2b is halogen, C1-C3fluoroalkyl, C1- C3fluoroalkoxy, or cyclopropyl. Preferably, R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; such as R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, trifluoromethyl, or difluoromethoxy, or R2b is chloro, bromo, 109921 | 83192 FF iodo, cyclopropyl, difluoromethyl, or trifluoromethyl. More preferably, R2b is chloro, bromo, difluoromethyl, trifluoromethyl, or difluoromethoxy, or cyclopropyl, or R2b is chloro, bromo, difluoromethyl, trifluoromethyl, or cyclopropyl; such as R2b is chloro, trifluoromethyl, difluoromethoxy, or cyclopropyl, or R2b is chloro, difluoromethyl, or cyclopropyl. For instance, R2b is difluoromethyl, trifluoromethyl, or difluoromethoxy, or R2b is trifluoromethyl or difluoromethoxy. [0048] In an embodiment of each aspect of the invention, R3 is as follows: A. R3 is C1-C3alkyl or C1-C3haloalkyl; or B. R3 is methyl or trifluoromethyl; or C. R3 is methyl. [0049] In preferred embodiments of each aspect of the invention, R3 is methyl. [0050] In an embodiment of each aspect of the invention, Q is Qa. In embodiments where Q is Qa, R5 is as follows: A. R5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkyloxy, or C3-C4cycloalkyl; or B. R5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or C. R5 is hydrogen, halogen, C1-C3alkyl, or C1-C3alkyloxy; or D. R5 is hydrogen, halogen, or C1-C3alkyloxy; or E. R5 is hydrogen, halogen, or C1-C3alkyl; or F. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, or ethoxy; or G. R5 is hydrogen, chloro, bromo, methyl, ethyl, cyclopropyl, methoxy, or ethoxy; or H. R5 is hydrogen, bromo, iodo, methyl, cyclopropyl; or I. R5 is hydrogen, chloro, bromo, iodo, methoxy, or ethoxy; or J. R5 is hydrogen, bromo, iodo, or cyclopropyl; or K. R5 is hydrogen, chloro, bromo, iodo, methyl, or ethyl; or L. R5 is hydrogen, chloro, bromo, or methyl; or M. R5 is hydrogen, chloro, or bromo; or N. R5 is hydrogen; or O. R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy [0051] In preferred embodiments where Q is Qa, R5 is hydrogen, chloro, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, or ethoxy; such as R5 is hydrogen, chloro, bromo, methyl, ethyl, cyclopropyl, or methoxy. Most preferably, R5 is hydrogen. [0052] For instance, Qa is selected from Qa-1, Qa-2, Qa-3, Qa-4, Qa-5, or Qa-6; Qa is selected from Qa-1, Qa- 3, Qa-4, Qa-5, Qa-6, or Qa-7; or Qa is selected from Qa-1, Qa-5, or Qa-6. Most preferably, Q is Qa-1: 109921 | 83192 FF [0053] In another embodiment of aspects of the invention where Q is Qb, R5a and R5b are as follows: A. R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkyloxy, or C3-C4cycloalkyl; or B. R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or C. R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, or C1-C3alkyloxy; or D. R5a and R5b are independently hydrogen, halogen, or C1-C3alkyloxy; or E. R5a and R5b are independently hydrogen, halogen, or C1-C3alkyl; or F. R5a and R5b are independently hydrogen, fluoro, chloro, bromo, iodo, methoxy, or ethoxy; or G. R5a and R5b are independently hydrogen, fluoro, chloro, bromo, iodo, or cyclopropyl; or H. R5a and R5b are independently hydrogen, fluoro, chloro, bromo, iodo, methyl, or ethyl; or I. R5a and R5b are independently hydrogen, fluoro, chloro, bromo, methyl, ethyl, cyclopropyl, methoxy, or ethoxy; or J. R5a and R5b are independently hydrogen, fluoro, chloro, methyl, cyclopropyl, or methoxy; or K. R5a and R5b are independently hydrogen, methyl, cyclopropyl, or methoxy; or L. R5a and R5b are differently hydrogen, chloro, methyl, cyclopropyl, or methoxy; or M. R5a or R5b is hydrogen, and the other is hydrogen, fluoro, chloro, methyl, cyclopropyl, or methoxy; or N. R5a and R5b are both hydrogen or fluoro; or O. R5a and R5b are hydrogen. [0054] In preferred embodiments where Q is Qb: A. R5a is hydrogen, chloro, fluoro, cyclopropyl, or methoxy; and R5b is hydrogen, fluoro, or methoxy; or B. R5a is hydrogen, fluoro, or cyclopropyl; and R5b is hydrogen, chloro, fluoro, or methoxy; or C. R5a is hydrogen, fluoro, or cyclopropyl; and R5b is hydrogen, fluoro, or methoxy; or D. R5a is hydrogen, fluoro, or cyclopropyl; and R5b is hydrogen; or 109921 | 83192 FF E. R5a is hydrogen; and R5b is hydrogen, fluoro, or methoxy; or F. R5a and R5b are hydrogen. [0055] For instance, Qb is selected from Qb-1 to Qb-10: [0056] As an example, Qb is selected from Qb-1, Qb-2, Qb-3, Qb-5, Qb-6, Qb-7, Qb-8, Qb-9, or Qb-10. Preferably, Qb is selected from Qb-1, Qb-3, Qb-5, Qb-6, Qb-7, Qb-9, or Qb-10; such as Qb is selected from Qb-1, Qb-3, Qb-5, Qb-7, Qb-9, or Qb-10. Most preferably, Qb is Qb-1. [0057] In embodiments where Q is Qa, R4 is as follows: A. R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4 is oxo-pyridazinyl optionally N- substituted with a single substituent R4c; or 109921 | 83192 FF F. R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6- cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5- bromopyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5- carbamoyl-thiazol-2-yl; or G. R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3- yl, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; or H. R4 is 5-cyano-2-pyridyl, or pyrimidin-2-yl; or I. R4 is 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, or 6-(methoxycarbonylamino)pyrimidin-4-yl; or J. R4 is Qc-9, preferably 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; or K. R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, or 5-cyanothiazol-2-yl; or L. R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5- chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 6-methoxypyridazin-3-yl, 5- carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; or M. R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4- yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5- carbamoyl-thiazol-2-yl; or 109921 | 83192 FF N. R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2-yl; or O. R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl,5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5- bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5- carbamoyl-thiazol-2-yl; or P. R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6- oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl. [0058] In preferred embodiments of each aspect of the invention, R4 is Qc-1, Qc-2, Qc-3, or Qc-9. More preferably, R4 is Qc-1, Qc-2, or Qc-9. For instance, R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2- yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5- carbamoyl-thiazol-2-yl; or R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin- 4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; such as preferably R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5- fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol- 2-yl; or R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, or 5-cyanothiazol-2-yl. [0059] In another preferred embodiments of each aspect of the invention, R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, or Qc-9 For instance, R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl,5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo- pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; and R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl. More preferably, R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo- pyridazin-3-yl, or 5-cyanothiazol-2-yl. [0060] In embodiments where Q is Qb, R4a is as follows: 109921 | 83192 FF A. R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo- pyridazinyl optionally N-substituted with a single substituent R4c; or B. R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, Qc-9, Qc-10, or Qc-11: C. R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, or Qc-9; or D. R4a is Qc-1, Qc-2, or Qc-9; or E. R4a is Qc-1; or F. R4a is 5-cyano-2-pyridyl, pyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6- (cyanomethylcarbamoyl)pyrimidin-4-yl, 6-[cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3- yl, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; or G. R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl; or H. R4a is 5-cyano-2-pyridyl. [0061] In preferred embodiments of each aspect of the invention, R4a is Qc-1, Qc-2, Qc-3, or Qc-9, such as R4a is Qc-1, Qc-2, or Qc-9. More preferably, R4a is Qc-1. [0062] In preferred embodiments of each aspect of the invention, the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, and oxo-pyridazinyl rings of R4 and R4a are each connected to the remainder of the compound via a carbon atom. In other words, a carbon atom of the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, or oxo-pyridazinyl rings of R4 and R4a is linked to Qa or Qb, respectively. [0063] In an embodiment of each aspect of the invention, R4b is as follows: A. R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; or B. R4b is hydrogen, halogen, cyano, hydroxy, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1- C3fluoroalkoxy, -C(O)NR10R11, or -NHC(O)R10; or 109921 | 83192 FF C. R4b is hydrogen, fluoro, chloro, iodo, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10 or - N(CH3)C(O)R10; or D. R4b is hydrogen, chloro, iodo, cyano, C1-C3alkyl, methoxy, -C(O)NR10R11, -NHC(O)R10 or - N(CH3)C(O)R10; or E. R4b is hydrogen, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10 or -N(CH3)C(O)R10; or F. R4b is hydrogen, cyano, C1-C3alkyl, methoxy, -C(O)NHR11, -NHC(O)R10 or -N(CH3)C(O)R10; or G. R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, - NHC(O)R10 or -N(CH3)C(O)R10; or H. R4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, - C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or I. R4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or J. R4b is hydrogen, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or K. R4b is hydrogen, cyano, -C(O)NH2, or -C(O)NHCH3; or L. R4b is hydrogen or cyano; or M. R4b is cyano, -C(O)NH2, or -C(O)NHCH3; or N. R4b is hydrogen; or O. R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, - C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or P. R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, - C(O)N(CH3)R11, -NHC(O)R10 or -N(CH3)C(O)R10; or Q. R4b is hydrogen, fluoro, chloro, bromo, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or R. R4b is hydrogen, fluoro, chloro, bromo, cyano, or -C(O)NH2; or S. R4b is hydrogen, fluoro, chloro, bromo, cyano, difluoromethyl, methoxy, or -C(O)NH2. [0064] In an embodiment of each aspect of the invention, for instance where Q is Qa-1 or Qb-1, R10 is as follows: A. R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or B. R10 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, cyclopropylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or C. R10 is hydrogen, C1-C3alkyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, cyanoC3- C4cycloalkyl, or C1-C3alkoxyC1-C3alkyl; or D. R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; or E. R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or cyanomethyl; or F. R10 is hydrogen, methyl, ethyl, isopropyl, or cyclopropyl; or G. R10 is hydrogen, methyl, or cyanomethyl; or H. R10 is hydrogen or methyl and R11 is as follows: 109921 | 83192 FF A. R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or B. R11 is hydrogen, hydroxy, C1-C3alkyl, C1-C3cyanoalkyl, cyanoC3-C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C3alkoxy; or C. R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, C1-C3cyanoalkyl, or C1-C3alkoxy; or D. R11 is hydrogen, C1-C3alkyl, cyanocyclopropyl, C1-C3alkoxyC1-C3alkyl, or methoxy; or E. R11 is hydrogen, C1-C3alkyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, or C1-C3alkoxy; or F. R11 is hydrogen, C1-C3alkyl, cyclopropyl, or C1-C3alkoxy; or G. R11 is hydrogen, C1-C3alkyl, cyclopropyl, or methoxy; or H. R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; or I. R11 is hydrogen or methyl; or J. R11 is hydrogen. [0065] In preferred embodiments of each aspect of the invention, R10 is hydrogen, methyl, or cyanomethyl, such as R10 is hydrogen or methyl. Also in embodiments of each aspect of the invention, R11 is hydrogen or methyl, such as R11 is hydrogen. [0066] In preferred embodiments of each aspect of the invention, R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or - NHC(O)OCH3; or R4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, - C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3. More preferably, R4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or R4b is hydrogen, fluoro, chloro, bromo, cyano, or -C(O)NH2. In another preferred embodiments of each aspect of the invention, R4b is hydrogen, fluoro, chloro, bromo, cyano, difluoromethyl, methoxy, or -C(O)NH2. [0067] In preferred embodiments of each aspect of the invention, the group R4b is in the meta or para position with respect to the link of R4 or R4a to the remainder of the compound, i.e. to the Qa or Qb ring, respectively. [0068] In an embodiment of each aspect of the invention, R4c is as follows: A. R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; or B. R4c is C1-C3alkyl, C1-C3haloalkyl, or C3-C6cycloalkylC1-C4alkyl; or C. R4c is methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl, or cyclopropylmethyl; or D. R4c is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl; or E. R4c is methyl, ethyl, or cyclopropylmethyl; or F. R4c is methyl or cyclopropylmethyl; or G. R4c is methyl or ethyl; or H. R4c is methyl. [0069] In preferred embodiments of each aspect of the invention, R4c is methyl or ethyl. For instance, R4c is methyl. 109921 | 83192 FF [0070] In more preferred embodiments of each aspect of the invention, R4 and R4a, as the case may be, are selected from QQ-1 to QQ-24, where the staggered line represents the connection to Qa or Qb: 109921 | 83192 FF [0071] Preferably, R4 and R4a, as the case may be, are selected from QQ-1, QQ-2, QQ-3, QQ-4, QQ-5, QQ- 6, QQ-7, QQ-8, QQ-9, QQ-10, QQ-11, QQ-12, QQ-13, QQ-15, QQ-18, QQ-19, QQ-20, and QQ-21; or R4 and R4a, as the case may be, are selected from QQ-1, QQ-2, QQ-3, QQ-4, QQ-5, QQ-6, QQ-7, QQ-8, QQ-9, QQ- 10, QQ-11, QQ-12, QQ-13, and QQ-15. More preferably, R4 and R4a are selected from QQ-1, QQ-2, QQ-9, QQ-18, QQ-19, QQ-20, and QQ-21; or R4 and R4a are selected from QQ-1, QQ-2, and QQ-9. Still preferably, R4 and R4a, as the case may be, are selected from QQ-1, QQ-2, QQ-3, QQ-5, QQ-9, QQ-13, QQ-15, QQ-18, QQ-19, QQ-20, QQ-21, QQ-22, QQ-23, and QQ-24. [0072] A preferred group of compounds of formula (I) is represented by compounds of formula (I-A): wherein A, R1, R2a, R2b and Q are as defined for compound of formula (I); or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula (I-A). More preferably, A is CH. [0073] Accordingly, the present invention makes available a compound of formula (I) having the substituents A, Q (i.e. Qa with R4 and R5, or Qb with R4a, R5a and R5b), R1, R2a, R2b, R3, R10, R11, and X as defined above, in all combinations and each permutation. [0074] For instance, compounds of formula (I) are made available, where A is CH or N; X is an oxygen atom or a sulfur atom; Q is Qa or Qb; R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a is hydrogen, C1-C4alkyl, C1- C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R2b is hydrogen, 109921 | 83192 FF halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1-C3alkylsulfinyl, C1- C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1- C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3-C4cycloalkylcarbonyl, or C3- C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, cyano, C1-C3alkyl, and C1-C3haloalkyl; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4 is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo- pyridazinyl optionally N-substituted with a single substituent R4c; R4b is hydrogen, halogen, cyano, hydroxy, C1- C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, -C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; R4c is C1- C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3-C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1-C3alkoxyC1- C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy. [0075] Compounds of formula (I) are made available, where A is CH or N; X is oxygen or sulfur; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1- cyanocyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qa; R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2-yl; and R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy. [0076] Compounds of formula (I) are made available, where A is CH or N; X is oxygen or sulfur; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1- cyanocyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qa; R4 is pyrimidin-2-yl, 5- cyano-2-pyridyl, or 5-cyanothiazol-2-yl; and R5 is hydrogen. [0077] Compounds of formula (I) are made available, where A is N; X is oxygen; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is C1-C3alkyl, C1-C3fluoroalkyl, cyclopropyl, or cyclopropyl substituted with a single fluoro or cyano; R2b is halogen, C1-C3fluoroalkyl, C1-C3fluoroalkoxy, or cyclopropyl; R3 is methyl or trifluoromethyl; Q is selected from Qa-1, Qa-2, Qa-3, Qa-4, Qa-5, Qa-6, or Qa-7; preferably Q is selected from Qa- 1, Qa-3, Qa-4, Qa-5, Qa-6, or Qa-7; and R4 is Qc-1, Qc-2, or Qc-9; such as R4 is 5-cyano-2-pyridyl, 5-carbamoyl- 2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6- cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5- bromopyrazin-2-yl, 6-methoxypyridazin-3-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5- cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl. 109921 | 83192 FF [0078] Compounds of formula (I) are made available, where A is N; X is oxygen; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is C1-C3alkyl, C1-C3fluoroalkyl, cyclopropyl, or cyclopropyl substituted with a single fluoro or cyano; R2b is halogen, C1-C3fluoroalkyl, C1-C3fluoroalkoxy, or cyclopropyl; R3 is methyl or trifluoromethyl; Q is selected from Qa-1, Qa-2, Qa-3, Qa-4, Qa-5, or Qa-6; preferably Q is selected from Qa-1, Qa- 5, or Qa-6; and R4 is Qc-1, Qc-2, or Qc-9; such as R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5- bromopyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5- carbamoyl-thiazol-2-yl. [0079] Preferably, compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1- cyanocyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qa; R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2-yl; and R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy. [0080] Compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qa; R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, or 5- cyanothiazol-2-yl; and R5 is hydrogen. [0081] More preferably, compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, or methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qa; R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5- chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-carbamoylpyrazin-2-yl, or 5-cyanothiazol-2-yl; and R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy. [0082] Compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, or methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qa; R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, or 5- cyanothiazol-2-yl; and R5 is hydrogen. [0083] Compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qb; R4a is pyrimidin-2-yl or 5-cyano-2-pyridyl; and R5a and R5b are hydrogen. 109921 | 83192 FF [0084] Compounds of formula (I) are also made available, where A is N; X is oxygen; R1 is hydrogen, methyl, or cyclopropyl-methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-cyanocyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl; Q is Qb; R4a is pyrimidin-2-yl or 5-cyano-2-pyridyl; and R5a and R5b are hydrogen. [0085] Compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, or methyl; R2a is hydrogen, methyl, ethyl, cyclopropyl; R2b is chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, or cyclopropyl; R3 is methyl; Q is Qa; R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin- 2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-(difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4- yl, pyrazin-2-yl, 6-methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl; and R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy. Synthesis [0086] Compounds of formula (I) can be prepared by those skilled in the art following known methods. More specifically compounds of formulae (I), (I’a) and (I-A), and intermediates therefor can be prepared as described below in the schemes and examples. Certain stereogenic centers have been left unspecified for the clarity and are not intended to limit the teaching of the schemes in any way. [0087] Compounds of formula (I), wherein Q, R1 and R3 are as defined in the first aspect, can be made, for example, as shown in scheme 1. Scheme 1 [0088] T represents have the same meaning as given for compounds of formula (I), and the staggered line represents the connection to the remainder of the compounds where T is attached to, such as the compounds of the formula (I), (Ia), (Ia-1), (Ib), (II), (IV), (IVa), (X), (XI) in Schemes 1 to 6 [0089] Compounds of the formula (I) can be made, for example, by reaction of a compound of the formula (II), wherein X1 is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride or fluoride, and wherein T has the meaning given above, with a compound of formula (III), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other 109921 | 83192 FF equivalent salt), wherein R1, R3 and Q have the same meaning as given above for compounds of the formula (I). In the case that X1 is hydroxy, it may be advantageous to carry out the reaction in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®). Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. Compounds of the formula (II) are either known, or they can be prepared by methods known to a person skilled in the art. In particular, compounds of the formula (II) wherein X1 is a leaving group, such as a halogen, for instance chloride or fluoride, can be formed by treatment of compounds of formula (II) wherein X1 is hydroxy with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), or a fluorinating agent, like diethylaminosulfur trifluoride (DAST), bis(2-methoxyethyl)aminosulfur trifluoride (deoxofluor™) or 2,4,6- trifluoro-1,3,5-triazine, in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around 25°C. Such methods are known to those skilled in the art and described for example in Tetrahedron 2005, 61 (46), 10827-10852. Scheme 2 [0090] Compounds of formula (III), or a salt thereof, wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I), can be made, for example, as shown in scheme 2. Treatment of a compound of the formula (V), wherein R3 and Q have the same meaning as given above for compounds of the formula (I) and X2 is a leaving group, such as a halogen or sulfonate, for instance bromide, with an amine of the formula (XIX), or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), gives compounds of the formula (III), wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. 109921 | 83192 FF [0091] Alternatively, treatment of a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), with an amine of the formula (XIX), or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), gives compounds of the formula (III), wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, for the alkylation of amines and for the reductive alkylation of amines (e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid, at room temperature, analogous to WO2002/088073; or alternatively, by the use of a combination of Ti(i- OiPr)4 and NaBH4 as described in Synthesis 2003 (14), 2206) are well known to a person skilled in the art. The amines of formula (XIX), or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. Scheme 3 [0092] Alternatively, compounds of formula (I) can be made, for example, by reaction of compound of the formula (IV), wherein T has the same meaning as given above in Scheme 1, and R1 has the same meaning as given above for compounds of the formula (I), with a compound of the formula (V), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), and X2 is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide. The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. Such methods for the alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art. [0093] Alternatively, a compound of the formula (I) can be made by reaction of a compound of the formula (IVa), wherein T has the same meaning as given above in Scheme 1, with a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, 109921 | 83192 FF with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods for the reductive alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art. Scheme 4 [0094] Compounds of formula (V), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), and X2 is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide, can be made, for example, as shown in scheme 4. Treatment of a compound of the formula (VIII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), with a halogenating agent, such as chlorine, bromine, N-chlorosuccinimide or N-bromosuccinimide, for example, gives compound of the formula (V), wherein the leaving group X2 is a halogen, for instance chloride or bromide. This reaction is done with or without a solvent, preferably in a solvent, with or without an additive, such as a radical starter, such as, for example, benzoyl peroxide or azoisobutyronitrile. The reaction can be done with or without exposure to visible light, or to UV light, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. [0095] Alternatively, a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), can be treated with a reducing agent, followed by reaction with a sulfonyl chloride, for instance methanesulfonyl chloride, to give a compound of the formula (V), wherein the leaving group X2 is a sulfonate, for instance a mesylate. This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. A suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods for the halogenation, the reduction of carbonyl compounds and the sulfonylation of alcohols, and the range of conditions to perform them, are well known to a person skilled in the art. The compounds of the formula (VII) and the compounds of formula (VIII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. 109921 | 83192 FF Scheme 5 [0096] Alternatively, compounds of formula (Ia-1), wherein T has the same meaning as given above in Scheme 1, and R1, R3 and Q have the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, can be made, for example, as shown in scheme 5. A compound of the formula (Ia), wherein T has the same meaning as given above in Scheme 1, and R3 and Q have the same meaning as given above for compounds of the formula (I), can be reacted with a compound of the formula (VI), wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X30 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula (Ia-1). This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. Such methods for the alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art and are described for example in WO2021/083936. Compounds of the formula (VI), wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X30 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, are either known, or they can be prepared by methods known to a person skilled in the art. 109921 | 83192 FF Scheme 6 [0097] Compounds of formula (Ib), wherein T has the same meaning as given above in Scheme 1, and R3, R4 and R5 have the same meaning as given above for compounds of the formula (I), can be made, for example, as shown in scheme 6. Reaction of a compound of the formula (II), wherein T has the same meaning as given above in Scheme 1 and wherein X1 is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride or fluoride, with a compound of the formula (IX), or a salt thereof, wherein R3 has the same meaning as given above for compounds of the formula (I), gives a compound of the formula (X), wherein T has the same meaning as given above in Scheme 1, and wherein R3 has the same meaning as given above for compounds of the formula (I). In the case that X1 is hydroxy, it may be advantageous to carry out the reaction in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0098] Subsequent treatment of compound of the formula (X), wherein T has the same meaning as given above in Scheme 1, R3 has the same meaning as given above for compounds of the formula (I), with the known compound (XIII), wherein R5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl (e.g. XIII is N,N-dimethylformamide dimethyl acetal, also named DMF-DMA), gives a compound of the formula (XI), wherein T has the same meaning as given above in Scheme 1, and wherein R3 has the same meaning as given above for compounds of the formula (I), and R5 is hydrogen, C1-C3alkyl, or C3-C4cycloalkyl. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 100 °C, or between ambient temperature and 50 °C, without a base or in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0099] Further reaction of compound of the formula (XI), wherein T has the same meaning as given above in Scheme 1, R3 has the same meaning as given above for compounds of the formula (I), and R5 is hydrogen, C1-C3alkyl, or C3-C4cycloalkyl, with a hydrazine compound of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 has the same meaning as given above for compounds of the formula (I), gives the compound of the formula (Ib), wherein T has the same meaning as given above in Scheme 1, R3 and R4 have the same meaning as given above for compounds of the formula (I), and R5 is hydrogen, C1-C3alkyl, or C3- C4cycloalkyl. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid, in a temperature 109921 | 83192 FF range of -100 to +300 °C, preferably between ambient temperature and 200 °C, or between ambient temperature and 80 °C. Within this sequence of transformations, the intermediate compounds of formula (X) and of formula (XI) can be used as crude products for the subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation. [0100] Compounds of the formula (IX), or a salt thereof, wherein R3 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. Hydrazine compounds of formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. [0101] Compounds of the formula (Ik) can be prepared by the reaction of an amine of the formula (IIIf), or a salt thereof wherein R1, R3, R4 and R5 are as described in formula (I), with a compound of the formula (IIa) wherein A, R2a and R2b are as described in formula (I) and X1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride or fluoride, under conditions already described in Scheme 1. 109921 | 83192 FF [0102] Compounds of formula (Ic) can be made, for example, as shown in scheme 7. Reaction of a compound of the formula (XVII) (wherein X05 is a leaving group such as chlorine, bromine, iodine, arysulfonate, alkylsulfonate or trifluoromethanesulfonate) with an amine of the formula (XIX), or a salt thereof, gives compounds of the formula (XVI), or a salt thereof. This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, for the reductive alkylation of amines are well known to a person skilled in the art. [0103] Subsequent reaction of the intermediate of the formula (XVI) , or a salt thereof, with a compound of the formula (IIa) gives a compound of the formula (XIV). This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. [0104] Subsequently, the intermediate of the formula (XIV) is reacted with a compound of the formula (XV) to give the compound of formula (Ic), wherein A, R2a, R2b, R1, R3 and R4a have the same meaning as given above for compounds of the formula (I), and M1 in R4a-M1 is a metal, such as for instance lithium, or –MgCl, or –ZnBr, or –B(OH)2; or R4a-M1 represents a boronate, such as a pinacol ester of a boronic acid, or a stannane such as R4a-Sn(n-Bu)3. Such transformations are known to a person skilled in the art as Suzuki-, Kumada-, 109921 | 83192 FF Negishi- or Stille-coupling reactions, respectively. Such reactions are carried out in a temperature range of - 100 to +300 °C, preferably between ambient temperature and 200 °C, in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst (for example palladium(II) acetate, 1,1’- bis(diphenylphosphino)ferrocene-palladium(II)dichloride or tetrakis(triphenyl-phosphine)palladium(0)), and optionally in the presence of an additional ligand, such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand. The reaction can be done in the presence or absence of an additional metal catalyst, such as, for example, a copper salt, for instance CuI. The reaction is done with or without a base, which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or tribasic potassium phosphate, or an organic base, such as an amine base, for instance triethyl amine. This reaction is done with or without a solvent, preferentially in a solvent, such as tetrahydrofuran, 2- methyltetrahydrofuran, acetonitrile, toluene or N,N-dimethylformamide, optionally in the presence of water. Where the reaction mixture is heated, the reaction can be conducted under microwave irradiation or with conventional heating, such as heating the reaction vessel in an oil bath. [0105] By an alternative route, compound (XVII) can be reacted with a compound of the formula (XV) to give intermediate (XVIII). This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate (XIV) to the compound of formula (Ic). [0106] Subsequently, the intermediate (XVIII) is reacted with a compound of the formula (IVb) to give a compound of the formula (Ic), wherein R1 is hydrogen and A, R2a, R2b, R3 and R4a have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound (XVII) to intermediate (XVI). [0107] By yet another alternative route, the intermediate compound of the formula (XVIII) can be reacted with an amine of the formula (XIX), or a salt thereof, to give the intermediate of the formula (IIIa), or a salt thereof. This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound (XVII) to intermediate (XVI). [0108] Subsequently, the intermediate of the formula (IIIa), or a salt thereof, is reacted with a compound of the formula (IIa) to give the compound of the formula (Ic), wherein A, R2a, R2b, R1, R3 and R4a have the same meaning as given above for compounds of the formula (I). This reaction is done essentially under the same conditions as described above for the transformation of intermediate (XVI) to intermediate (XIV). [0109] Within these different multistep sequences, the intermediate compounds of formulas (XIV), (XVI), (XVIII) and (IIIa) can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation. Compounds of the formula (XVII) are known, or they can be prepared by methods known to a person skilled in the art. [0110] Compounds of the formula (Id) 109921 | 83192 FF can be prepared by the reaction of an amine of the formula (IIIb), or a salt thereof wherein R1, R3, R4a, R5a and R5b are as described in formula (I), with a compound of the formula (IIa) wherein A, R2a and R2b are as described in formula (I) and X1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride or fluoride, under conditions already described in Scheme 1. [0111] The chemistry is described in more detail in Scheme 8. Scheme 8 [0112] Reaction of a compound of the formula (IIa), wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride or fluoride, with a compound of formula (IIIb), or a salt thereof, gives a compound of the formula (Id), wherein A, R2a, R2b, R1, R3, R4a, R5a and R5b have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such 109921 | 83192 FF as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. [0113] The formation of compounds of formula (IIIb) is outlined in Scheme 9. Scheme 9 [0114] Compounds of formula (IIIb), or a salt thereof, can be prepared by treatment of compounds of formula (IIIc), or a salt thereof, wherein R3, R4a, R5a, and R5b are as described in formula (I), with compounds of formula (XX), wherein R1a is, for example, H, methyl or cyclopropyl, e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid, at room temperature analogously to WO2002/088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206). [0115] Amines of formula (IIIc), or a salt thereof, may be obtained by biocatalyzed deracemization of amines of formula (IIId), or a salt thereof. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert- butyl ether at temperatures between 20 °C to 100 °C. Such processes are described for instance in J. Org. Chem. 2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization are known of those skilled in the art and are documented in the literature, for instance in J. Org. Chem. 1991, 56, 2656-2665 or J. Am. Chem. Soc. 2015, 137, 3996−4009. [0116] In an alternative process, compounds of formula (IIIc), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be obtained from compounds of the formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I), following the synthesis described in Scheme 10. Scheme 10 109921 | 83192 FF [0117] Amines of formula (IIIc), or a salt thereof, may be obtained from intermediates of formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9. [0118] Such intermediates of formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXI), wherein R3, R4a, R5a, and R5b are as described in formula (I), by a Mitsunobu reaction, which involves treating alcohols of formula (XXI) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and of an amine such as phthalimide (HNPhth) or bis(tert-butoxycarbonyl)amine(HNBoc2). Mitsunobu reactions are known by those skilled in the art to proceed with inversion of the stereocenter, as described for instance in Chem. Rev. 2009, 109, 2551-2651. [0119] Alternatively, amines of formula (IIIc) may be obtained by reduction of azides of formula (XXIII), wherein R3, R4a, R5a, and R5b are as described in formula (I), by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula (XXIII) may be obtained by treatment of alcohols of formula (XXI), wherein R3, R4a, R5a, and R5b are as described in formula (I), with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU. Such processes are known by those skilled in the art to proceed with inversion of the stereocenter and are described in the literature for instance in Adv. Synth. Catal. 2018, 360, 2157–2165. [0120] Alcohols of formula (XXI) may be obtained by enantioselective reduction of ketones of formula (XXIV), wherein R3, R4a, R5a, and R5b are as described in formula (I). Such reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4. Such processes are described in the literature for instance in J. Org. Chem.2017, 82, 5607. [0121] Alternatively, compounds of formula (IIIc) may also be prepared as outlined in Scheme 11. 109921 | 83192 FF [0122] Amines of formula (IIIc), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be prepared by deprotection of amines of formula (XXV), wherein R3, R4a, R5a, and R5b are as described in formula (I), for instance using an acid such as trifluoroacetic acid or hydrochloric acid, optionally in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane. [0123] Amines of formula (XXV) can be obtained by condensation of diamines of formula (XLVII), wherein R5a, and R5b are as described in formula (I), on diketones of formula (XXVI), wherein R3 and R4a are as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ. [0124] Diketones of formula (XXVI) may be formed by oxidation of hydroxyketones of formula (XXVII), wherein R3 and R4a are as described in formula (I). This oxidation can involve for instance SO3-pyridine in presence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/Bu4NHSO4. Examples of such oxidations can be found in the literature, for instance in Synlett, 2014, 25, 596 or J. Am. Chem. Soc.1990, 112, 5290-5313. [0125] Hydroxyketones of formula (XXVII) may be synthesized by cross-benzoin condensation between aldehydes of formula (XXIX), wherein R4a is as described in formula (I), and aldehydes of formula (XXVIII), wherein R3 is as described in formula (I). [0126] Aldehydes of formula (XXVIII) are commercially available in chiral form, like for instance Boc-L- alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36- 9). Cross-benzoin condensations are done in the usual way by employing an organocatalyst such as a triazolium salt or a thiazolium salt, in the presence of a base such as potassium tert-butoxide or N,N- isopropylethylamine, in a suitable solvent such as DCM or THF, at a temperature between -20 °C and the 109921 | 83192 FF boiling point of the solvent. Examples of catalysts for such transformations have been described in the literature for instance in J. Am. Chem. Soc. 2014, 136, 7539-7542 or in Org. Lett. 2016, 18, 4518-4521. [0127] As shown in Scheme 12, compounds of formula (Id) can be alternatively prepared by reaction of compounds of formula (XXX) (wherein A, R2a, R2b, R1, R3, R5a and R5b are as defined in formula (I) and X07 is a leaving group like, for example, chlorine, bromine, iodine) with compounds of formula (XXXI) (Stille reaction; R4a in XXXI is as defined in formula I) or compounds of formula (XXXII) (Suzuki-Miyaura reaction; R4a in XXXII is as defined in formula (I) and W is a boronic acid B(OH)2 group, or a corresponding boronate, such as a pinacol ester of said boronic acid) in the presence of a palladium catalyst as described in detail in Scheme 7. [0128] Compounds of formula (XXX) can be prepared by coupling of amines of formula (XXXIII) and compounds of formula (IIa), wherein A, R2a, R2b and X1 are described in Scheme 1, under the conditions described in detail in Scheme 1. Under the same conditions, if R1 = H, compounds of formula (XXX) may be obtained directly from compounds of formula (XXXIV). [0129] Compounds of formula (XXXIII) can be prepared by treatment of compounds of formula (XXXIV), with compounds of formula (XX) (wherein R1a is, for example, H, methyl or cyclopropyl), e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid, at room temperature, in an analogous 109921 | 83192 FF way as described in WO2002/088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206). [0130] Amines of formula (XXXIV) can be prepared by deracemization procedure method, which involves for example, a selective acylation of one enantiomer. Such an example is described in Scheme 13 more in OTf Scheme 13 [0131] Amines of formula (XXXIV) may be obtained by biocatalyzed deracemization of amines of formula (XXXIVa), wherein R3, R5a, and R5b are as in formula (I) and X07 is a leaving group such as bromine, chlorine or iodine. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether at temperatures between 20 °C to 100 °C. Such processes are described for instance in J. Org. Chem.2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization are known of those skilled in the art and are documented in the literature, for instance in J. Org. Chem. 1991, 56, 2656-2665 or J. Am. Chem. Soc. 2015, 137, 3996−4009. [0132] Alternatively, resolution of amines of formula (XXXIVa) to give amines of formula (XXXIV) may be achieved using a chiral auxiliary, as described in Scheme 14. Scheme 14 [0133] Amines of formula (XXXIV) can be prepared from intermediates of formula (XXXVII), wherein R3, R5a, and R5b are as in compounds of the formula (I), X07 is a leaving group such as bromine, chlorine or iodine, and X12* is a chiral auxiliary, by treatment with acids such as HCl or bases such as NaOH. Chiral auxiliaries of 109921 | 83192 FF formula (XXXVI) are for instance mandelic acid or (1R)-menthylchloroformate. Intermediates of formula (XXXVII) can be formed by coupling of a chiral auxiliary of formula (XXXVI), wherein X0 is a leaving group, such as chlorine, with amines of the formula (XXXIVa) following the conditions detailed in Scheme 1. Examples of such deracemization processes are reported in the literature, for instance in J. Org. Chem.2007, 72, 485-493. [0134] Alternatively, amines of formula (XXXIV), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be formed as described in Scheme 15. Scheme 15 [0135] Amines of formula (XXXIV), or a salt thereof, may be obtained from intermediates of formula (XXIIa), wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (when Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (when Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9. [0136] Such intermediates of formula (XXIIa), wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXIa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction, which involves treating alcohols of formula (XXIa) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and of an amine such as phthalimide(HNPhth) or bis(tert-butoxycarbonyl)amine (HNBoc2). Mitsunobu reactions are known by those skilled in the art to proceed with inversion of the stereocenter, as described for instance in Chem. Rev. 2009, 109, 2551-2651. [0137] Alternatively, amines of formula (XXXIV) may be obtained by reduction of azides of formula (XXIIIa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or 109921 | 83192 FF sulfonate, for instance bromide, by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula (XXIIIa) may be obtained by treatment of alcohols of formula (XXIa) with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU. Such processes are known by those skilled in the art to proceed with inversion of the stereocenter and are described in the literature for instance in Adv. Synth. Catal. 2018, 360, 2157–2165. [0138] Alcohols of formula (XXIa) may be obtained by enantioselective reduction of ketones of formula (XXIVa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide. Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p- cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4. Such processes are described in the literature for instance in J. Org. Chem.2017, 82, 5607. [0139] As shown above in Scheme 16, compounds of the formula (I’a), a subset of compounds of the formula (I), wherein A, R1, R2a, R2b, R3 and Q are as defined for compounds of the formula (I), can be prepared by reaction of compounds of the formula (IIa-1), a subset of compounds of the formula (II) wherein A, R2a and R2b are as described in formula (I) and X1 is hydroxy, with either compounds of the formula (IIIf) or (IIIb), or a salt thereof, under conditions already described above (transformations IIa + IIIf to Ik, and IIa + IIIb to Id) and in Scheme 1. [0140] Compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I), can be prepared by saponification of compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under conditions known to a person skilled in the art (using for example conditions such as: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane at room temperature, or up to refluxing conditions; or alternatively treating compounds of the formula (IIa-2) with an acid, such as for example a hydrohalide acid, preferably hydrochloric or hydrobromic acid, or trifluoroacetic acid, optionally in presence of a solvent, such as tetrahydrofuran, dioxane or dichloromethane, at temperatures between 0°C and 150°C). [0141] Compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by means of a carbonylation reaction on compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), in the presence of an alcohol RaOH, wherein Ra is C1-C6alkyl or benzyl. Typically in such a carbonylation reaction, the compounds of formula (XL) are reacted with carbon monoxide CO (usually under pressure, for example in the range of 5 to 200 bar), in the presence 109921 | 83192 FF of a metal catalyst such as a palladium catalyst (for example: palladium(II) acetate, or 1,1’- bis(diphenylphosphino)ferrocene-palladium(II)dichloride (Pd(dppf)Cl2, optionally as a dichloromethane complex)), optionally in the presence of a phosphine ligand, preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine, in an alcohol RaOH solvent (optionally in presence of an inert organic co-solvent), and at temperatures ranging between 0°C and 250°C, preferably between room temperature and 200°C. [0142] Alternatively, compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I), can be prepared by i. performing a lithium-halogen (Li-X3) exchange on compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), followed by ii. quenching the formed organolithium species with carbon dioxide. Such lithium-halogen exchange reactions can be performed using, for example, organolithium compounds such as butyllithium (BuLi), in an anhydrous aprotic solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran or N,N′-dimethylpropylene-urea (DMPU), and at temperatures ranging from -120°C to 0°C, preferably between -78 and 0°C. The formed lithiated intermediate is preferably quenched in situ with carbon dioxide (gaseous, or alternatively solid carbon dioxide known as dry ice) to generate the compounds of the formula (IIa-1). Similar reactions are reported in literature for example in WO 2006/013048. Scheme 17 [0143] As shown above in Scheme 17, compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by treating compounds of the formula (L), wherein A, R2a and R2b are as described in formula (I), with a halogenation reagent, for example, just to cite a few common reagents, N-chloro succinimide, N-bromo succinimide or N-iodo succinimide. Other halogenation reagents can also be used, as for example bromine. The reaction can be performed in an inert solvent like acetonitrile or acetic acid at a temperature usually comprised between 0°C and 80°C. Depending on the reactivity of the compounds (L), addition of a stronger acid, like trifluoroacetic acid, can facilitate the reaction. 109921 | 83192 FF [0144] Compounds of formula (L) can be obtained by cyclization of compounds of formula (LI), wherein A, R2a and R2b are as described in formula (I). In this reaction a cyclic urea is formed from two neighboring amino groups. For this purpose, reagents like phosgene, diphosgene, triphosgene or carbonyl diimidazole, for example, can be used. The reaction can usually be performed around.0°C to ambient temperature or at higher temperature for di- and triphosgene, in an inert anhydrous solvent, like toluene, ethyl acetate or chloroform. The compounds of formula (LI), in turn, can be obtained by reduction of the nitro group of compounds of the formula (LII), wherein A, R2a and R2b are as described in formula (I). Nitro to amino reduction is very common in organic synthesis and can be performed under a multitude of conditions. Some examples will be cited here: catalytic reduction with hydrogen over a palladium containing catalyst (usually on charcoal) in an inert solvent or reduction with a metal like iron powder in presence of an acid like hydrochloric acid or acetic acid or ammonium chloride. This reaction is usually performed in a mixture of water and an organic cosolvent, like ethanol, at a temperature between 0°C and the boiling temperature of the solvent. Tin(II)chloride can also be used for reducing the nitro group. Compounds or the formula (LII) can be prepared by reacting compounds of the formula R2a-NH2 (LIV), or a salt thereof, wherein R2a is as described in formula (I), with compounds of the formula (LIII), wherein A and R2b are as described in formula (I) and X4 is a leaving group, like, for example a halogen atom, preferably bromine, chlorine or iodine (even more preferably chlorine). X4 can also be a leaving group like a sulfonate, for example a triflate, or an alkylsulfonyl or arylsulfonyl group, like Me-SO2- or benzenesulfonyl. This reaction can be performed with an excess of (LIV), acting as a base or in presence of another non-reactive base, like Hünig’s base or triethylamine or a carbonate, like cesium carbonate or a phosphate, like trisodium phosphate or in the presence of a metal hydride, like sodium hydride. This substitution is facilitated by the presence of the neighboring nitro group. There are many commercially available compounds of the formula (LIII), and many others have been described in the literature or can be prepared by analogy. Compounds of the formula (LIV), or a salt thereof, are also available or can be accessed by the person skilled in the art of organic synthesis. [0145] A particular selection of compounds of formula (I’a), wherein R1, R2a, R2b, R3 and Q are as defined for compounds of formula (I) and A is CH and X is O, is represented by compounds of formula (I’A). [0146] These compounds can be prepared (scheme 18) from compounds of formula (IIA-1), wherein R1, R2a, R2b and R3 are as defined for compounds of formula (I), in an analogous way as was shown in scheme 16. 109921 | 83192 FF Scheme 18 [0147] As depicted in scheme 19, compounds of the formula (IIA-1), wherein R2a and R2b are as defined in formula (I), may be obtained from compounds of the formula (LV), wherein R2a and R2b are as defined in formula (I) and Ar is an aromatic group, preferably phenyl, 4-tolyl, 4-chlorophenyl or 4-bromophenyl, under oxidative conditions, for example, aqueous potassium permanganate. [0148] The compounds of formula (LV) can be obtained from the reaction of compounds of the formula (LVI), wherein R2a and R2b are as defined in formula (I) and Ar is an aromatic group as defined hereabove. The cyclization can be performed with a wide variety of reagents, for example phosgene, diphosgene, triphosgene or carbonyl diimidazole. The reaction is usually performed in an aprotic solvent, like toluene or a chlorinated hydrocarbon, like chloroform, dichloromethane, 1,2-dichloroethane. The presence of a base, as for example triethylamine or 4-dimethylaminopyridine, might be desirable, especially if there is formation of an acid as byproduct. The reaction can be performed between 0°C and the boiling temperature of the reaction mixture, depending on the reactivity of the reagent used. [0149] The compounds of the formula (LVI), wherein R2a and R2b are as defined in formula (I) and Ar is an aromatic group as defined hereabove can be obtained by the reduction of the nitro group into an amine function. This type of transformation is very common in the chemical processes and can be performed using a wide range of conditions and reagents. Some examples are hydrogen over palladium (0) on charcoal or iron powder in presence of an acid (this process is also known as Béchamp reaction), or tin (II) chloride. Many of these conditions have already been evoked in scheme 17.
109921 | 83192 FF Scheme 19 [0150] The compounds of the formula (LVII), wherein R2a and R2b are as defined in formula (I) and Ar is an aromatic group as defined hereabove can be obtained by the cleavage of the protecting group of compounds of the formula (LVIII), wherein R2a and R2b are as defined in formula (I), Ar is an aromatic group as defined hereabove and PG is a protecting group resistant to alkaline and nucleophilic conditions, like methoxymethyl, benzyl, 4-methoxybenzyl, tetrahydrofuran-2-yl or tetrahydropyran-2-yl. This protecting group, depending on its nature, can be removed under acidic conditions, like trifluoroacetic acid or catalytic reduction (hydrogen over palladium on carbon, for example), or oxidative conditions. It might even be advantageous to perform the deprotection and the nitro reduction of compounds of the formula (LVIII) to yield in one step compounds of the formula (LVI). [0151] The compounds of the formula (LVIII), as described hereabove can be obtained by reacting compounds of formula (LIX), wherein R2a and R2b are as defined in formula (I) and PG is a protecting group as described hereabove, with a compound of the formula (LXII), wherein Ar is an aromatic group as defined hereabove. This type of reaction is called vicarious nucleophilic substitution and is performed with an excess of a strong base, often powdered potassium hydroxide or t-BuOK, in a polar solvent, like dimethyl sulfoxide or 109921 | 83192 FF tetrahydrofuran. More details can be found in the following literature: M. Makosza et al; Tetrahedron (1984), 40(10), 1863-1868. [0152] The compounds of the formula (LIX), wherein R2a and R2b are as defined in formula (I) and PG is a protecting group as described hereabove, can be obtained by derivatizing the nitrogen atom of compounds of the formula (LX), wherein R2a and R2b are as defined in formula (I). Preferred methods are using a base in presence of an optionally substituted benzylic halide or sulfonate, for benzyl or 4-methoxybenzyl introduction (given as examples) or for reacting with chloromethyl methyl ether, or under acid catalysis with dihydrofuran or dihydropyran. These conditions are well known to the person skilled in the art of chemical synthesis and are very well described, for example in Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9. [0153] Compounds of formula (LX), wherein R2a and R2b are as defined in formula (I), can be prepared by reacting compounds of the formula (LXI), wherein R2b is as defined in formula (I) and X5 is a leaving group, as for example a halide, preferably fluoride or chloride, or a sulfonate, like triflate, mesylate or tosylate with an amine compounds of formula (LIV), or a salt thereof, wherein R2a is as defined in formula (I). The leaving group X5 is activated towards nucleophilic substitution by the neighboring nitro group. This reaction is preferably performed in presence of a base like sodium hydride or cesium carbonate, in a solvent like dimethylformamide or acetonitrile, at temperatures comprised between 0°C and the boiling point of the reaction mixture, preferably around room temperature. [0154] Many compounds of the formulae (LIX), (LXI) and (LXII) used for the synthesis hereabove are commercially available and described in the literature or can be prepared in an analogous way. [0155] Certain compounds of formula (III), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or any other equivalent salt), wherein R1, R3 and Q have the same meaning as given above for compounds of the formula (I), are known in the literature. [0156] For example, compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above, wherein R1, R3, R4a, R5a and R5b are as described in formula (I), particularly those compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above, wherein R3 and R4a are as described in formula (I) and in which R1, R5a and R5b are hydrogen, can be prepared in analogy to descriptions found for example in WO 2021/083936, WO 2021/069575, and WO 2022/258481. [0157] Similarly, compounds of the formula (IIIe) and (IIIf), or a salt thereof as defined above, wherein R1, R3, R4 and R5 are as described in formula (I), particularly those compounds of the formula (IIIe) and (IIIf), or a salt thereof as defined above, wherein R3 and R4 are as described in formula (I) and in which R1 is hydrogen 109921 | 83192 FF or methyl and R5 is hydrogen, methyl or cyclopropyl, can be prepared in analogy to descriptions found for example in WO 2021/083936, WO 2021/099303, WO 2021/105091, WO 2021/165195, WO 2021/224323, WO 2022/268648, WO 2023/104714 and WO 2023/247360. [0158] In particular, compounds of the formula (IIIg), wherein R1, R3, R5, R10 and R11 are as described in formula (I) can be prepared according to reactions outlined in Scheme 20. Scheme 20 [0159] As shown in Scheme 20, compounds of the formula (IIIg), wherein R1, R3, R5, R10 and R11 are as described in formula (I), can be prepared from compounds of formula (IIIg-1), wherein R1, R3, R5, R10 and R11 are as described in formula (I), and X- is an anion, by treatment with a base, such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin. Such procedures are well known to a person skilled in the art and known from the literature and textbooks. The anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic 109921 | 83192 FF acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid. A great number of such acids are known to a person skilled in the art. [0160] Compounds of formula (IIIg-1), wherein R1, R3, R5, R10 and R11 are as described in formula (I), and X- is an anion, can be made from compounds of the formula (IIIg-2), wherein R1, R3, R5, R10 and R11 are as described in formula (I), by treatment with an acid, such as the acids listed above. The reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents. The reaction can be done in a temperature range between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at ambient temperature. [0161] Compounds of the formula (IIIg-2), wherein R1, R3, R5, R10 and R11 are as described in formula (I), can be prepared by reacting compounds of the formula (IIIg-3), or a salt thereof, wherein R1, R3, R5 and R11 are as defined for compounds of the formula (I), with compounds of the formula X6-C(O)OR10 (XL-b), wherein R10 is as defined for compounds of the formula (I) and X6 is halogen, preferably chlorine, in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, N,N-diisopropylethylamine or pyridine, optionally in the presence of a catalyst (such as 4-dimethylaminopyridine DMAP), in an inert solvent such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene, at temperatures between 0 and 50°C, under standard amide bond formation conditions known to a person skilled in the art. Certain bases, such as pyridine and triethylamine, may be employed successfully as both base and solvent. [0162] Compounds of the formula (IIIg-3), or a salt thereof, wherein R1, R3, R5 and R11 are as defined for compounds of the formula (I), can be prepared from compounds of the formula (IIIg-4), wherein R1, R3 and R5 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), by treatment with amine compounds of the formula H2NR11 (XL-a), or a salt thereof, wherein R11 is as defined for compounds of the formula (I), optionally in the presence of a copper catalyst, such as copper powder, copper(I) iodide or copper sulfate, or mixtures thereof, optionally in the presence of a ligand, for example a diamine ligand (e.g. trans-cyclohexyldiamine) or 1,10-phenanthroline, optionally in the presence of a base, such as sodium, potassium or cesium carbonate, or potassium phosphate, in inert solvents such as alcohols, amides, esters, ethers, nitriles and water, particularly preferred are methanol, ethanol, 2,2,2- trifluoroethanol, propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, water or mixtures thereof, at temperatures between 0-150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally under microwave irradiation or pressurized conditions using an autoclave. In the particular amination reaction featuring amine compound of the formula H2NR11 (XL-a), wherein R11 is hydrogen (i.e. H2NR11 is ammonia), it may be advantageous to use ammonium hydroxide (solution of ammonia in water), a solution of ammonia in inert organic solvents, such as ethyl acetate, dioxane or methanol, or ammonia surrogates such as ammonium salts (for instance ammonium chloride). 109921 | 83192 FF [0163] Alternatively, compounds of the formula (IIIg-2), wherein R1, R3, R5, R10 and R11 are as described in formula (I), may be prepared by reacting compounds of the formula (IIIg-4), wherein R1, R3 and R5 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), with compounds of the formula HN(R11)C(O)OR10 (XL-c), wherein R10 and R11 are as defined for compounds of the formula (I), optionally in the presence of a catalyst, for example palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, optionally in form of a chloroform adduct), or a palladium pre-catalyst such as for example tert-BuBrettPhos Pd G3 [(2-Di-tert-butylphosphino-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2′-amino-1,1′- biphenyl)]palladium(II) methanesulfonate or BrettPhos Pd G3 [(2-di-cyclohexylphosphino-3,6-dimethoxy- 2′,4′,6′- triisopropyl-1,1′-biphenyl)-2-(2′-amino-1,1′ -biphenyl)]palladium(II) methanesulfonate, and optionally in the presence of a ligand, for example BINAP, SPhos, t-BuBrettPhos or Xantphos, in the presence of a base, such as sodium, potassium or cesium carbonate, sodium hydroxide or potassium phosphate, in an inert solvent, such as tetrahydrofuran, 2-methyl-tetrahydrofuran, dioxane, toluene, N,N-dimethylformamide, N,N- dimethylacetamide, N-methyl pyrrolidine or dimethyl sulfoxide, at temperatures between 60-180°C, optionally under microwave irradiation. [0164] Compounds of the formula (IIIg-4), wherein R1, R3 and R5 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), can be prepared by reacting compounds of the formula (IIIg-5), wherein R1, R3 and R5 are as defined for compounds of the formula (I), with hydrazine compounds of the formula (XII-1) or a tautomer thereof, or a salt thereof, wherein Xa is a halogen, preferably Br or Cl (even more preferably Cl), under analogous conditions already described above in Scheme 6 (transformation XI + XII into Ib). [0165] Compounds of the formula (IIIg-5), wherein R1, R3 and R5 are as defined for compounds of the formula (I), are known, for instance from WO2021/083936 or WO2021/165195, or they can be made in analogy to descriptions found therein. Compounds of the formula (XII-1) or a tautomer thereof, or a salt thereof, wherein Xa is a halogen, preferably Br or Cl (even more preferably Cl), are known or even commercially available, or they can be made by known methods. [0166] In particular, compounds of the formula (IIIh), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared according to reactions outlined in Scheme 21.
109921 | 83192 FF [0167] Compounds of the formula (IIIh), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared from compounds of formula (IIIh-1), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), and X- is an anion, by treatment with a base, such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin. Such procedures are well known to a person skilled in the art and known from the literature and textbooks. The anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid. A great number of such acids are known to a person skilled in the art. [0168] Compounds of formula (IIIh-1), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), and X- is an anion, can be made from compounds of the formula (IIIh-2), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), by treatment with an acid, such as the acids listed above. The reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents. The reaction can be done in a temperature range between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at ambient temperature. [0169] Compounds of the formula (IIIh-2), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared by reaction of compounds of the formula (XII-2), or a tautomer thereof, or a salt thereof, wherein X5 is a halogen, preferably Br, Cl or I (even 109921 | 83192 FF more preferably Br or Cl), with a compound of the formula (IIIg-5), wherein R1, R3 and R5 are as defined for compounds of the formula (I). The reaction can be done neat, or in a solvent, for instance an organic solvent, such as dioxane or acetic acid, or a mixture thereof. The reaction can be performed in the presence or in the absence of a drying agent, such as for example in the presence of molecular sieves, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 80 °C. [0170] Compounds of the formula (XII-2), or a tautomer thereof, or a salt thereof, wherein X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), are known or even commercially available, or they can be made by known methods. [0171] Alternatively, compounds of the formula (IIIf-1), wherein R1, R4 and R5 are as defined for compounds of the formula (I), or a salt thereof (IIIf-2), in which X- is an anion as defined above in Scheme 21 (compounds of the formula (IIIf-1) are representatives of compounds of the formula (IIIf) in which R3 is CH3), can be made (Scheme 22) from compounds of the formula (IIIf-3), wherein R1, R4 and R5 are as defined for compounds of the formula (I), following the chemistry and conditions described above in Scheme 21 (transformation IIIh-2 into IIIh via IIIh-1). Scheme 22 [0172] Compounds of the formula (IIIf-3), wherein R1 and R4 are as defined for compounds of the formula (I), and in which R5 is hydrogen or C1-C3alkyl, can be prepared by reacting compounds of the formula (IIIg- 5), in which R3 is CH3 and wherein R1 is as defined for compounds of the formula (I) and R5 is hydrogen or C1- C3alkyl, with hydrazine compounds of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 is as defined for compounds of the formula (I), under analogous conditions already described above in Scheme 6 (transformation XI + XII into Ib). [0173] Alternatively, compounds of the formula (IIIf-3), wherein R1 and R4 are as defined for compounds of the formula (I), and in which R5 is C1-C3alkyl or C3-C4cycloalkyl, can be prepared by reacting compounds of the formula (IIIf-4), wherein R1 is as defined for compounds of the formula (I) and R5 is C1-C3alkyl or C3- C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, with hydrazine compounds of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 is as defined for compounds of the formula (I), under analogous conditions 109921 | 83192 FF already described above in Scheme 6 (transformation XI + XII into Ib) or detailed in J Org Chem, 2011, 76, 1177-1179. [0174] Compounds of the formula (IIIf-4), wherein R1 is as defined for compounds of the formula (I) and R5 is C1-C3alkyl or C3-C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, can be prepared by reacting compounds of the formula (IIIf-5), wherein R1 is as defined for compounds of the formula (I), with compounds of the formula (IIIf-6) or a tautomer thereof, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R5 is C1-C3alkyl or C3- C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, in the presence of a coupling reagent, such as, for example, HATU (1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium), PyBOP (benzotriazol-1- yloxytripyrrolidinophosphonium hexafluorophosphate) or propanephosphonic acid cyclic anhydride (T3P®). Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N- dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. Such conditions are described for example in J Org Chem, 2011, 76, 1177-1179. [0175] Compounds of the formula (IIIf-5), wherein R1 is as defined for compounds of the formula (I), are known or even commercially available, or they can be made by known methods. [0176] Compounds of the formula (IIIf-6) or a tautomer thereof, or a salt thereof, wherein R5 is C1-C3alkyl or C3-C4cycloalkyl, and RL is -NH2 (compound IIIf-6 is an alkyl or cycloalkyl amidine, for example cyclopropanecarboxamidine) or -OC1-C4alkyl (compound IIIf-6 is an alkyl or cycloalkyl imidate, for example ethyl propanimidate), are known or even commercially available, or they can be made by known methods. Scheme 23 [0177] Alternatively, compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared (Scheme 23) by cyclization of compounds of the formula (LI-1), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under analogous conditions already described above in Scheme 17 (transformation LI into L, cyclization). [0178] Compounds of the formula (LI-1), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by reduction of compounds of the formula (LII-1), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under analogous conditions already described above in Scheme 17 (transformation LII into LI, nitro reduction). 109921 | 83192 FF [0179] Compounds of the formula (LII-1), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by reacting compounds of the formula (LIII-1), wherein A and R2b are as described in formula (I), X4 is a leaving group, like, for example a halogen atom, preferably bromine, chlorine or iodine (even more preferably chlorine), or alternatively X4 is a leaving group like a sulfonate, for example a triflate, or an alkylsulfonyl or arylsulfonyl group, like Me-SO2- or benzenesulfonyl, and in which Ra is C1-C6alkyl or benzyl, with compounds of the formula R2a-NH2 (LIV), or a salt thereof, wherein R2a is as described in formula (I), under analogous conditions already described above in Scheme 17 (transformation LIII into LII, amination). [0180] Compounds of the formula (LIII-1), wherein A and R2b are as described in formula (I), X4 is a leaving group, like, for example a halogen atom, preferably bromine, chlorine or iodine (even more preferably chlorine), or alternatively X4 is a leaving group like a sulfonate, for example a triflate, or an alkylsulfonyl or arylsulfonyl group, like Me-SO2- or benzenesulfonyl, are known or even commercially available, or they can be made by known methods. [0181] Compounds of the formula (LII-3), wherein A and R2a are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, form a particular subset of compounds of the formula (LII-1), wherein R2b is difluoromethoxy. Scheme 24 [0182] Such compounds of the formula (LII-3) can be prepared (Scheme 24) by difluoromethylation of compounds of the formula (LII-2), wherein A and R2a are as described in formula (I), and in which Ra is C1- C6alkyl or benzyl, under conditions known to a person skilled in the art. Typically, compounds of the formula (LII-2) are reacted with a :CF2 carbene species, generated from difluoromethylating agents such a difluoroacetate XcCF2COONa or a difluoromethyl(phosphonate) XcCF2P(O)(OEt)2 reagent, wherein Xc can be chloro or bromo, in the presence of a base such as for example sodium or potassium carbonate, or sodium or potassium hydroxide, in an appropriate solvent like for example acetonitrile, Ν,Ν-dimethylformamide or N- methyl-2-pyrrolidone (NMP), optionally in a mixture with water, optionally in the presence of an additive (such as 2'-hydroxyacetophenone), and at temperature between -40°C to 80°C. Such methods have been described in the literature, for example in Org. Lett.2013, 15(19), 5036-5039; Tetrahedron 2009, 65(27), 5278-5283; or Chem. Commun.2017, 53, 5706. [0183] Compounds of the formula (LII-2), wherein A and R2a are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by reacting compounds of the formula (LII-1), wherein A and R2a are as described in formula (I), and R2b is a halogen, preferably F, Cl, or Br, and in which Ra is C1-C6alkyl or benzyl, with for example benzaldoxime PhC=NOH, preferably (E)-benzaldehyde oxime, in the presence of a 109921 | 83192 FF base, such as potassium or cesium carbonate, optionally in the presence of a palladium catalyst (in that instance R2b is preferably Cl or Br) such as RockPhos-G3-palladacycle ([(2-Di-tert-butylphosphino-3- methoxy-6-methyl-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2-aminobiphenyl)]palladium(II) methanesulfonate), in an aprotic solvent such as acetonitrile or N,N-dimethylformamide DMF, at temperatures between 0 and 100°C, preferably between room temperature and 80°C, as described, for example, in Angew. Chem. Int. Ed. 56 (16), 4478–4482, 2017. [0184] Alternatively, compounds of the formula (LII-2), wherein A and R2a are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by reacting compounds of the formula (LII-1), wherein A and R2a are as described in formula (I), and R2b is a halogen, preferably F, Cl, or Br (more preferably F), and in which Ra is C1-C6alkyl or benzyl, with 2-(methylsulfonyl)ethanol, in the presence of a base, such as sodium hydride, in an inert solvent, such as Ν,Ν-dimethylformamide or N-methyl-2-pyrrolidone (NMP), at temperatures between 0°C and 80°C, preferably around 0°C. The in situ generated compound of the formula (LII-1), wherein R2b is hydroxyl protected by 2-(methylsulfonyl)ethyl (via aromatic nucleophilic substitution), may be isolated. However, preferred is a process where above reaction mixture is subjected to acid deprotection conditions, such as treating with aq. HCl under stirring, preferably under cooling conditions, to directly afford compounds of the formula (LII-2). [0185] Depending on the procedure or the reaction conditions, the reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N- dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU). [0186] The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N- methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. [0187] The reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C. [0188] Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent 109921 | 83192 FF according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step. [0189] Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent. [0190] Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent. [0191] Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture. [0192] Depending on the procedure or the reaction conditions, the compounds of formula (I), which have salt-forming properties can be obtained in free form or in the form of salts. [0193] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case. [0194] Diastereomer mixtures or racemate mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography. [0195] Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this 109921 | 83192 FF manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents. [0196] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry. [0197] N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000/15615. [0198] It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity. [0199] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form. [0200] The compounds of formula (I) according to the following Tables A-1 to A-30 and Tables B-1 to B-5 can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula (I- A) and (I-B). Tables A-1 to A-30 (formula I-A) [0201] Table A-1 provides 20 compounds A-1.001 to A-1.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. For example, compound A-4.011 is 109921 | 83192 FF [0202] Table A-2 provides 20 compounds A-2.001 to A-2.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0203] Table A-3 provides 20 compounds A-3.001 to A-3.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0204] Table A-4 provides 20 compounds A-4.001 to A-4.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0205] Table A-5 provides 20 compounds A-5.001 to A-5.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0206] Table A-6 provides 20 compounds A-6.001 to A-6.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0207] Table A-7 provides 20 compounds A-7.001 to A-7.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0208] Table A-8 provides 20 compounds A-8.001 to A-8.020 of formula I-A wherein R2a is CH3, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0209] Table A-9 provides 20 compounds A-9.001 to A-9.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0210] Table A-10 provides 20 compounds A-10.001 to A-10.020 of formula I-A wherein R2a is CH3, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0211] Table A-11 provides 20 compounds A-11.001 to A-11.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0212] Table A-12 provides 20 compounds A-12.001 to A-12.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0213] Table A-13 provides 20 compounds A-13.001 to A-13.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0214] Table A-14 provides 20 compounds A-14.001 to A-14.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0215] Table A-15 provides 20 compounds A-15.001 to A-15.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0216] Table A-16 provides 20 compounds A-16.001 to A-16.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0217] Table A-17 provides 20 compounds A-17.001 to A-17.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0218] Table A-18 provides 20 compounds A-18.001 to A-18.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0219] Table A-19 provides 20 compounds A-19.001 to A-19.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0220] Table A-20 provides 20 compounds A-20.001 to A-20.020 of formula I-A wherein R2a is CH2CH3, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. 109921 | 83192 FF [0221] Table A-21 provides 20 compounds A-21.001 to A-21.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0222] Table A-22 provides 20 compounds A-22.001 to A-22.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0223] Table A-23 provides 20 compounds A-23.001 to A-23.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0224] Table A-24 provides 20 compounds A-24.001 to A-24.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0225] Table A-25 provides 20 compounds A-25.001 to A-25.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0226] Table A-26 provides 20 compounds A-26.001 to A-26.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0227] Table A-27 provides 20 compounds A-27.001 to A-27.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0228] Table A-28 provides 20 compounds A-28.001 to A-28.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0229] Table A-29 provides 20 compounds A-29.001 to A-29.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0230] Table A-30 provides 20 compounds A-30.001 to A-30.020 of formula I-A wherein R2a is Cyp, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. Table Z: Substituent definitions of Q 109921 | 83192 FF [0231] In Tables A-1 to A-30, Cyp represents cyclopropyl. 109921 | 83192 FF Tables B-1 to B-5 (formula I-B) [0232] Table B-1 provides 19 compounds B-1.001 to B-1.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H, R5 is CH3 and R4x are as defined in table Z1. [0233] Table B-2 provides 19 compounds B-2.001 to B-2.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H, R5 is CH2CH3 and R4x are as defined in table Z1. [0234] Table B-3 provides 19 compounds B-3.001 to B-3.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H, R5 is cyclopropyl and R4x are as defined in table Z1. [0235] Table B-4 provides 19 compounds B-4.001 to B-4.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H, R5 is OCH3 and R4x are as defined in table Z1. [0236] Table B-5 provides 19 compounds B-5.001 to B-5.019 of formula I-B wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H, R5 is Br and R4x are as defined in table Z1. Table Z1: Substituent definitions of R4x 109921 | 83192 FF [0237] In Tables B-1 to B-5, Cyp represents cyclopropyl. [0238] Also made available are certain intermediate compounds as shown in Schemes 1 to 20, some of which are novel. For example: ^ A compound of formula IIa-1, as shown below, where A, R2a and R2b are as defined for compounds of formula (I); for instance, where A, R2a and R2b are as described in Tables A-1 to A-30 and Tables B-1 to B-5; in particular where A is CH, R2a is cyclopropyl, and R2b is chloro, bromo, difluoromethoxy, difluoromethyl, or trifluoromethyl, preferably difluoromethoxy, difluoromethyl, or trifluoromethyl; ^ A compound of formula IIa-2, as shown below, where A, R2a and R2b are as defined for compounds of formula (I), and Ra is C1-C6alkyl or benzyl, preferably Ra is methyl or ethyl; for instance, where A, R2a and R2b are as described in Tables A-1 to A-30 and Tables B-1 to B-5, in particular where A is CH, R2a is cyclopropyl, and R2b is chloro, bromo, difluoromethoxy, difluoromethyl, or trifluoromethyl, preferably difluoromethoxy, difluoromethyl, or trifluoromethyl. 109921 | 83192 FF [0239] The following compounds are listed in the CAS database, and therefore are not an aspect of the invention: - 2,3-Dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid; - Methyl 2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Methyl 6-fluoro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - 2,3-Dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylic acid - Methyl 2,3-dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 2,3-dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylate - 2,3-Dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylic acid - 6-Bromo-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 2,3-Dihydro-2-oxo-6-(trifluoromethyl)-1H-benzimidazole-4-carboxylic acid - 1-Ethyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - Methyl 1-ethyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - 2,3-Dihydro-6-methoxy-2-oxo-1H-benzimidazole-4-carboxylic acid - 6-Chloro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 6-Fluoro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - Ethyl 2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Methyl 6-chloro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 6-chloro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 6-fluoro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 6-bromo-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - 1-(2-Fluoro-1-methylethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic - Methyl 6-chloro-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate acid - Ethyl 6-bromo-1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 6-bromo-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 6-chloro-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate - Methyl 6-bromo-1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate - Ethyl 2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate - Methyl 2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate - 6-Bromo-2,3-dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylic acid - 6-Bromo-1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - Methyl 6-bromo-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate - 1-(3-Fluoropropyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 2,3-Dihydro-2-oxo-1-(2,2,3,3-tetrafluoropropyl)-1H-benzimidazole-4-carboxylic acid - 1-(2-Fluoroethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 6-Bromo-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylic acid - 6-Chloro-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylic acid 109921 | 83192 FF - 2,3-Dihydro-2-oxo-1-(2,2,2-trifluoroethyl)-1H-benzimidazole-4-carboxylic acid - 2,3-Dihydro-1-(1-methylpropyl)-2-oxo-1H-benzimidazole-4-carboxylic acid - 1-Cyclobutyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 1-(2,2-Difluoroethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 1-(1,1-Dimethylethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 2,3-Dihydro-2-oxo-1-propyl-1H-benzimidazole-4-carboxylic acid - 1-Cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid - 2,3-Dihydro-1-(2-methylpropyl)-2-oxo-1H-benzimidazole-4-carboxylic acid - 1-Butyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid Pest control [0240] The compounds of formula (I) according to the invention are preventively and/or curatively valuable ac-tive ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate. [0241] Examples of the above mentioned animal pests are: ^ from the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; ^ from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; ^ from the order Coleoptera, for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae spp., Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.; 109921 | 83192 FF ^ from the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; ^ from the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp. , Thyanta spp , Triatoma spp., Vatiga illudens, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae , Unaspis citri, Zygina flammigera, Zyginidia scutellaris ; ^ from the order Hymenoptera, for example, Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; ^ from the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminata; 109921 | 83192 FF ^ from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.; ^ from the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; ^ from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp., and Schistocerca spp.; ^ from the order Psocoptera, for example, Liposcelis spp.; ^ from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; ^ from the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; ^ from the order Thysanura, for example, Lepisma saccharina. [0242] In a further aspect, the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; 109921 | 83192 FF Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.. [0243] The compounds of the invention may also have activity against the molluscs. Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides. [0244] The active ingredients according to the invention can be used for controlling, i.e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests. [0245] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coco-nut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family and latex plants. [0246] The compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens. [0247] For example the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia 109921 | 83192 FF spp. (e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants. [0248] For example the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba. [0249] Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber. [0250] The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice). [0251] The compounds of formula (I) are particularly suitable for control of ^ a pest of the order Hemiptera, for example, one or more of the species Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in vegetables, soybeans, and sugarcane); 109921 | 83192 FF ^ a pest of the order Lepidoptera, for example, one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta (preferably in vegetables and corn); ^ a pest of the order Thysanoptera, such as the family Thripidae, for example, one or more of Thrips tabaci and Frankliniella occidentalis (preferably in vegetables); and ^ soil pests (such as of the order Coleoptera), for example, the species Diabrotica balteata, Agriotes spp. and Leptinotarsa decemlineata (preferably in vegetables and corn). [0252] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. [0253] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases. [0254] In the context of the present invention there are to be understood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). [0255] Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073. [0256] The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic 109921 | 83192 FF acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401979 and WO 90/13651. [0257] The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera). [0258] Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1FA2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); Nature-Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®. [0259] Further examples of such transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. 109921 | 83192 FF 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 × MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. [0260] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch). [0261] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818 and EP-A-0353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. [0262] Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens. [0263] Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode. [0264] Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art. [0265] Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related proteins" (PRPs; see e.g. EP-A-0392225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906). [0266] Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and 109921 | 83192 FF also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type. [0267] The present invention provides a compound of the first aspect for use in therapy. The present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal. The present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal. The present invention further provides a compound of the first aspect, for use in preventing and/or treating diseases transmitted by ectoparasites. [0268] The present invention provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and/or treating diseases transmitted by ectoparasites. [0269] The present invention provides the use of a compound of the first aspect, in controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal. [0270] The term "controlling" when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and/or preventing further pest or parasite infestation. [0271] The term "treating" when used in context of parasites in or on an animal refers to restraining, slowing, stopping or reversing the progression or severity of an existing symptom or disease. [0272] The term "preventing" when used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal. [0273] The term "animal" when used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and companion animals. Livestock animals include, but are not limited to, cattle, camelids, pigs, sheep, goats and horses. Companion animals include, but are not limited to, dogs, cats and rabbits. [0274] A "parasite" is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense. An "endoparasite" is a parasite which lives in the host animal. An "ectoparasite" is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice). The Acari (or Acarina) sub-class comprises ticks and mites. Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates. Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and 109921 | 83192 FF Homoptera. Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis. Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola ovis and Bovicola bovis. [0275] The term "effective amount" when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal. The effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of involvement or the severity of the disease or disorder; the response of the individual; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances. [0276] The compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally' and subcutaneously. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip. In the alternative, the compounds of the invention may be administered by means of an ear tag or collar. [0277] Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts. Pharmaceutically and veterinary acceptable salts and common methodology for preparing them are well known in the art. See, for example, Gould, P.L., "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201 -217 (1986); Bastin, R.J., et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4: 427-435 (2000); and Berge, S.M., et al., "Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66: 1-19, (1977). One skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as a salt, such as a hydrochloride salt, using techniques and conditions well known to one of ordinary skill in the art. In addition, one skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as the corresponding free base from the corresponding salt. [0278] The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method 109921 | 83192 FF of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents. [0279] In one embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents. [0280] Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005/113886 or WO 2007/090739. [0281] Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees. [0282] In the field of tree injection/trunk treatment, the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A. Examples of exotic woodborers of economic importance. Family Species Host or Crop Infested Buprestidae Agrilus planipennis Ash Cerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandrus crassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperda Conifers Table B. Examples of native woodborers of economic importance. Family Species Host or Crop Infested Buprestidae Agrilus anxius Birch Agrilus politus Willow, Maple Agrilus sayi Bayberry, Sweetfern 109921 | 83192 FF Family Species Host or Crop Infested Agrilus vittaticolllis Apple, Pear, Cranberry, Serviceberry, Hawthorn Chrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry, Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut, Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum, Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texania campestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplar Cerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak, Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytus acuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Eastern hophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust, Honeylocust, Yellow-poplar, Chestnut, Osage- orange, Sassafras, Lilac, Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood, Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleaf hackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant, Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood, Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, Mulberry Oncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood, Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit trees Saperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory, Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak, Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, Elm 109921 | 83192 FF Family Species Host or Crop Infested Dendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wild cherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut, Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, Pine Phloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry, Mountain-ash Pseudopityophthorus Oak, American beech, Black cherry, Chickasaw pruinosus plum, Chestnut, Maple, Hickory, Hornbeam, Hophornbeam Sesiidae Paranthrene simulans Oak, American chestnut Sannina uroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine, Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum, Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedon scitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Black cherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark, Bayberry Vitacea polistiformis Grape [0283] The present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs, ticks, spittlebugs, southern chinch bugs and white grubs. The present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults. [0284] In particular, the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M. castanea) and Tomarus spp., ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.). 109921 | 83192 FF [0285] The present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis). [0286] The present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs. [0287] The present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf. [0288] In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas. [0289] Examples of such parasites are: ^ Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.. ^ Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.. ^ Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.. ^ Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. ^ Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. ^ Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.. ^ Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.. ^ Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., 109921 | 83192 FF Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.. [0290] The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings. [0291] The compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spp., Tryptodendron spp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spp., and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina. [0292] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P”) controls one or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. [0293] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp. [0294] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P”) controls one or more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp. [0295] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis. [0296] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P”) controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis 109921 | 83192 FF craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella + TX, Nilaparvata lugens + TX, Myzus persicae + TX, Chrysodeixis incIudens + TX, Aphis craccivora + TX, Diabrotica balteata + TX, Rhopalosiphum Padi + TX, and Chilo suppressalis + TX. [0297] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops. [0298] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P is suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice). [0299] Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability). In particular, it has been surprisingly found that certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera. [0300] The following combinations of a compound of formula I with another active substance in a weight ratio of 1:1 are preferred (where the abbreviation “TX” means "one compound selected from the compounds defined in Tables A-1 to A-30 and Tables B-1 to B-5, and Table P”): [0301] (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)- dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec- 13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, 1-(4-chlorophenyl)-2-fluoro-4-methyl-5-(2,2,2- trifluoroethylsulfanyl)benzene + TX, 1,2-dibromo-3-chloropropane + TX, 1,2-dichloropropane + TX, 1,2- dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 14-methyloctadec-1-ene + TX, 1- hydroxy-1H-pyridine-2-thione + TX, 2-(octylthio)ethanol + TX, 2-[5-(2-chloro-3,3,3-trifluoro-prop-1-enyl)-1- methyl-imidazol-2-yl]-5-cyclopropyl-3-ethylsulfonyl-pyridine + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 4- (quinoxalin-2-ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5- methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, 109921 | 83192 FF acynonapyr + TX, Adoxophyes orana GV + TX, afidopyropen + TX, afoxolaner + TX, Agrobacterium radiobacter + TX, AKD-3088 + TX, alanycarb + TX, aldicarb + TX, aldoxycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + TX, alpha-multistriatin + TX, Amblyseius spp. + TX, amidoflumet + TX, amino acids + TX, aminocarb + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, Autographa californica NPV + TX, AZ 60541 + TX, azadirachtin + TX, azocyclotin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus sp. AQ175 (ATCC Accession No. 55608) + TX, Bacillus sp. AQ177 (ATCC Accession No.55609) + TX, Bacillus sp. AQ178 (ATCC Accession No.53522) + TX, Bacillus sphaericus Neide + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B- 50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) + TX, Bacillus subtilis unspecified + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No B-21530) + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. Aizawai + TX, Bacillus thuringiensis subsp. Israelensis + TX, Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thurin-giensis subsp. Tenebrionis + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, Beauveria brongniartii + TX, benclothiaz + TX, benomyl + TX, bensultap + TX, bentioflumin (CAS Number: 2566451-67-8) + TX, benzoximate + TX, benzpyrimoxan + TX, betacyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, bioresmethrin + TX, bis(tributyltin) oxide + TX, bisazir + TX, bistrifluron + TX, bisulflufen + TX, brevicomin + TX, broflanilide + TX, brofluthrinate + TX, bromoacetamide + TX, bromophos-ethyl + TX, bronopol + TX, busulfan + TX, butocarboxim + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butylpyridaben + TX, cadusafos + TX, calcium arsenate + TX, carbaryl + TX, carbofuran + TX, carbon disulfide + TX, carbosulfan + TX, cartap + TX, CAS number: 1594624-87-9 + TX, CAS number: 1922957-47-8 + TX, CAS number: 1255091-74-7 + TX, CAS number: 1365070-72-9 + TX, CAS Number: 158062-71-6 + TX, CAS number: 1594626-19-3 + TX, CAS number: 1594637-65-6 + TX, CAS number: 1632218-00-8 + TX, CAS number: 1808115-49-2 + TX, CAS number: 1922957-46-7 + TX, CAS number: 1922957-48-9 + TX, CAS number: 1956329-03-5 + TX, CAS number: 1990457-52-7 + TX, CAS number: 1990457-55-0 + TX, CAS number: 1990457-57-2 + TX, CAS number: 1990457-66-3 + TX, CAS number: 1990457-77-6 + TX, CAS number: 1990457-85-6 + TX, CAS number: 2032403-97-5 + TX, CAS number: 2044701-44-0 + TX, CAS number: 2095470-94-1 + TX, CAS number: 2128706-05-6 + TX, CAS number: 2133042-31-4 + TX, CAS number: 2133042-44-9 + TX, CAS number: 2171099-09-3 + TX, CAS number: 2220132-55-6 + TX, CAS number: 2396747-83-2 + TX, CAS number: 2408220-91-5 + TX, CAS number: 2408220-94-8 + TX, CAS number: 2415706-16-8 + TX, CAS Number: 2583740-14-9 + TX, CAS Number: 2583751-98-6 + TX, CAS number: 2719848-60-7 + TX, CAS Number: 2898489-71-7 + TX, CAS Number: 2922115-20-4 + TX, CAS Number: 3060345-80-1 + TX, CAS Number: 3061364-30-2 + TX, CAS Number: 34763-86-5 + TX, CAS number: RNA (Leptinotarsa decemlineata- 109921 | 83192 FF specific recombinant double-stranded interfering GS2) + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chloropicrin + TX, chloroprallethrin + TX, chlorpyrifos + TX, chromafenozide + TX, Chrysoperla carnea + TX, clenpirin + TX, cloethocarb + TX, clothianidin + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper dioctanoate + TX, copper hydroxide + TX, copper sulfate + TX, cresol + TX, crufomate + TX, Cryptolaemus montrouzieri + TX, cuelure + TX, cyanofenphos + TX, cyantraniliprole + TX, cybenzoxasulfyl (CAS Number: 2128706-04-5) + TX, cybutryne + TX, cyclaniliprole + TX, cyclobutrifluram + TX, cycloprothrin + TX, cycloxaprid + TX, Cydia pomonella GV + TX, cyenopyrafen + TX, cyetpyrafen + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cylohalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyproflanilide + TX, cyromazine + TX, cytokinins + TX, Dacnusa sibirica + TX, dazomet + TX, DBCP + TX, DCIP + TX, deltamethrin + TX, diafenthiuron + TX, dialifos + TX, diamidafos + TX, dibrom + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dichlofenthion + TX, dichlone + TX, dichlorophen + TX, dicliphos + TX, dicloromezotiaz + TX, diethyltoluamide + TX, diflubenzuron + TX, Diglyphus isaea + TX, dimatif + TX, dimethoate + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimpropyridaz + TX, dinactin + TX, dinocap + TX, dinotefuran + TX, dioxabenzofos + TX, dipyrithione + TX, disparlure + TX, D-limonene + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8,10-dien-1-yl acetate + TX, dodicin + TX, dominicalure + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, empenthrin + TX, Encarsia formosa + TX, endothal + TX, endrin + TX, eprinomectin + TX, epsilon - momfluorothrin + TX, epsilon- metofluthrin + TX, Eretmocerus eremicus + TX, esfenvalerate + TX, ethion + TX, ethiprole + TX, ethoprophos + TX, ethyl 4-methyloctanoate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, etofenprox + TX, etoxazole + TX, etpyrafen + TX, eugenol + TX, Extract of seaweed and fermentation product derived from melasse + TX, Extract of seaweed and fermentation product derived from melasse comprising urea + TX, Extract of seaweed and fermented plant products + TX, Extract of seaweed and fermented plant products comprising phytohormones, vitamins, EDTA-chelated copper, zinc, and iron + TX, famphur + TX, fenaminosulf + TX, fenamiphos + TX, fenazaquin + TX, fenfluthrin + TX, fenitrothion + TX, fenmezoditiaz + TX, fenobucarb + TX, fenothiocarb + TX, fenoxycarb + TX, fenpropathrin + TX, fenpyrad + TX, fenpyroximate + TX, fensulfothion + TX, fenthion + TX, fentin + TX, fentinacetate + TX, fenvalerate + TX, ferric phosphate + TX, fipronil + TX, flometoquin + TX, flonicamid + TX, fluacrypyrim + TX, fluazaindolizine + TX, fluazuron + TX, flubendiamide + TX, flubenzimine + TX, fluchlordiniliprole + TX, flucitrinate + TX, flucycloxuron + TX, flucythrinate + TX, fluensulfone [318290-98-1] + TX, fluensulfone + TX, flufenerim + TX, flufenprox + TX, flufiprole + TX, fluhexafon + TX, flumethrin + TX, fluopyram + TX, flupentiofenox + TX, flupyradifurone + TX, flupyrimin + TX, flupyroxystrobin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, formaldehyde + TX, fosthiazate + TX, fosthietan + TX, frontalin + TX, furfural + TX, galquin (CAS Number: 2644770-30-7) + TX, gamma-cyhalothrin + TX, Gossyplure® (1:1 mixture of the (Z,E) and (Z,Z) isomers of hexadeca-7,11-dien- 1-yl-acetate) + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, Granulovirus + TX, guadipyr + TX, GY-81 + TX, halfenprox + TX, halofenozide + TX, Harpin + TX, Helicoverpa armigera Nucleopolyhedrovirus + TX, Helicoverpa zea NPV + TX, Helicoverpa zea Nucleopolyhedrovirus + TX, Heliothis punctigera Nucleopolyhedrovirus + TX, Heliothis virescens Nucleopolyhedrovirus + TX, hemel + TX, hempa + TX, heptafluthrin + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexalure 109921 | 83192 FF + TX, hexamide + TX, hexythiazox + TX, Hippodamia convergens + TX, hydramethylnon + TX, hydrargaphen + TX, hydrated lime + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, Indazapyroxamet + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, ipsdienol + TX, ipsenol + TX, isamidofos + TX, isazofos + TX, isocycloseram + TX, Isoflualanam (CAS number: 2892524-05-7) + TX, isothioate + TX, ivermectin + TX, japonilure + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kinetin + TX, lambda-cyhalothrin + TX, ledprona + TX, lepimectin + TX, Leptomastix dactylopii + TX, lineatin + TX, litlure + TX, looplure + TX, lotilaner + TX, lufenuron + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, mecarphon + TX, medlure + TX, megatomoic acid + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Metarhizium spp. + TX, metepa + TX, methiocarb + TX, methiotepa + TX, methomyl + TX, methoquin-butyl + TX, methoxyfenozide + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methylneodecanamide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, milbemycin oxime + TX, momfluorothrin + TX, morzid + TX, moxidectin + TX, muscalure + TX, Muscodor albus 620 (NRRL Accession No. 30547) + TX, Muscodor roseus A3-5 (NRRL Accession No. 30548) + TX, Myrothecium verrucaria composition + TX, nabam + TX, NC-184 + TX, Neem tree based products + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca- 2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, ostramone + TX, oxamate + TX, oxamyl + TX, oxazosulfyl + TX, oxolinic acid + TX, oxytetracycline + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, parathion- ethyl + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, penfluron + TX, pentachlorophenol + TX, permethrin + TX, phenothrin + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, Phytoseiulus persimilis + TX, picaridin + TX, pioxaniliprole + TX, piperazine + TX, piperflanilide (CAS number: 2615135-05-0) + TX, piperonylbutoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, potassium and molybdenum and EDTA-chelated manganese + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, prallethrin + TX, probenazole + TX, profenofos + TX, profluthrin + TX, propargite + TX, propetamphos + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyrethrum + TX, pyridaben + TX, pyridalyl + TX, pyridin-4-amine + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyriminostrobin + TX, pyriprole [394730-71-3] + TX, pyriprole + TX, pyriproxyfen + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, quinoclamine + TX, quinonamid + TX, resmethrin + TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663) + TX, sarolaner + TX, S-bioallethrin + TX, sebufos + TX, selamectin + TX, siglure + TX, silafluofen + TX, simazine + TX, sodium pentachlorophenoxide + TX, sordidin + TX, spidoxamat + TX, spinetoram + TX, spinosad + TX, spirobudifen + TX, spirodiclofen + TX, spiromesifen + TX, spiropidion + TX, spirotetramat + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus + TX, Spodoptera 109921 | 83192 FF frugiperda Nucleopolyhedrovirus + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Streptomyces galbus (NRRL Accession No.30232) + TX, Streptomyces sp. (NRRL Accession No. B-30145) + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulfiflumin + TX, sulfoxaflor + TX, tazimcarb + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimiphos + TX, tecloftalam + TX, tefluthrin + TX, temephos + TX, tepa + TX, terbam + TX, terbufos + TX, terpenoid blend + TX, tetrachlorantraniliprole + TX, tetrachlorothiophene + TX, tetradec- 11-en-1-yl acetate + TX, tetradiphon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, tetraniliprole + TX, theta-cypermethrin + TX, thiacloprid + TX, thiafenox + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiosultap + TX, thiotepa + TX, tiapyrachlor (CAS Number: 1255091-74-7) + TX, tigolaner + TX, tiorantraniliprole + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, tretamine + TX, triazamate + TX, triazophos + TX, triazuron + TX, tributyltin oxide + TX, trichlorfon + TX, trichloronate + TX, trichlorphon + TX, Trichogramma spp. + TX, trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc-call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp. + TX, xylenols + TX, YI-5302 + TX, zeatin + TX, zeta-Cypermethrin + TX; N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1- benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-ethyl-N’-[5-methoxy-2- methyl-4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2019/110427) + TX, (3-methylisoxazol-5-yl)-[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds may be prepared from the methods described in WO 2017/220485) + TX, (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3- carboxylate (this compound may be prepared from the methods described in WO 2014/006945) + TX, (5- methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (7E,9Z)-dodeca-7,9- dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)- tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate, + TX, (R)-3-(difluoromethyl)-1-methyl- N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11- en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en- 10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707) + TX, (Z,2E)-5-[1-(4- chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, , [2-[3-[2-[1-[2-[3,5- bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1- (4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5- 109921 | 83192 FF a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6- trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3- dimethyl-isoquinoline (these compounds may be prepared from the methods described in WO2017/025510) + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2- dibromo-3-chloropropane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 10-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 1-bromo-2-chloroethane + TX, 1-dichloro-1-nitroethane + TX, 1-hydroxy- 1H-pyridine-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1- yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4-yl) pyridine- 3- carboxamide + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl- indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3- carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX, 2-(difluoromethyl)-N-[3- ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(octylthio)ethanol + TX, 2,2,2-trichloro-1-(3,4- dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2,2-difluoro- N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound may be prepared from the methods described in WO 2011/138281) + TX, 2-[2-fluoro-6-[(8-fluoro- 2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1- (1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2-imidazolidone + TX, 2-isovalerylindan- 1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-oxo-N-propyl-2-[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2018/065414) + TX, 2-thiocyanatoethyl laurate + TX, 3-(4,4-difluoro-3,3-dimethyl-1- isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds may be prepared from the methods described in WO2016/156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1- yl)quinolone + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3- trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-[2-(1- chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2- fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods 109921 | 83192 FF described in WO 2016/156290) + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6- trifluorophenyl)pyridazine + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro- biphenyl-2-yl)-amide + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1, 3- dimethyl- 1H- pyrazol- 5- amine + TX, 4-(2,6- difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6- fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 4,4- difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6- methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5- a]pyridin-3-yl)isoquinoline + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]isoxazolidin-3-one + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol- 1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl- 1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy- 3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-chloro-2-(2-chloro-2-methyl- propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, 4-chlorophenyl phenyl sulfone + TX, 4- methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl- pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6- chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4- carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-chloro-4,4-difluoro- 3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2- difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole- 3-carbonitrile + TX, 6-isopentenylaminopurine + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl- butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline- 3-carboxamide + TX, 8-hydroxyquinoline sulfate + TX, acethion + TX, acetoprole + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, acrylonitrile + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, aldoxycarb + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-chlorohydrin + TX, alpha-ecdysone + TX, alpha-multistriatin + TX, aluminium phosphide + TX, Amblyseius spp. + TX, amectotractin + TX, ametoctradin + TX, amidithion + TX, amidothioate + TX, aminocarb + TX, aminopyrifen + TX, amisulbrom + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, anabasine + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, ancymidol + TX, anilazine + TX, anisiflupurin + TX, anthraquinone + TX, antu + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, aramite + TX, arsenous oxide + TX, athidathion + TX, Autographa californica NPV + TX, azaconazole + TX, azamethiphos + TX, azobenzene + TX, azothoate + TX, azoxystrobin + TX, Bacillus sphaericus Neide + TX, 109921 | 83192 FF Bacillus thuringiensis delta endotoxins + TX, barium carbonate + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, Beauveria brongniartii + TX, benalaxyl + TX, benclothiaz + TX, benomyl + TX, benoxafos + TX, benthiavalicarb + TX, benzothiostrobin + TX, benzovindiflupyr + TX, benzyl benzoate + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, bis(tributyltin) oxide + TX, bisazir + TX, bisthiosemi + TX, bitertanol + TX, bixafen + TX, blasticidin-S + TX, borax + TX, bordeaux mixture + TX, boscalid + TX, brevicomin + TX, brodifacoum + TX, brofenvalerate + TX, bromadiolone + TX, bromethalin + TX, bromfenvinfos + TX, bromoacetamide + TX, bromocyclen + TX, bromo-DDT + TX, bromophos + TX, bromopropylate + TX, bromuconazole + TX, bronopol + TX, bufencarb + TX, bupirimate + TX, buprofezin + TX, busulfan + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, butacarb + TX, butathiofos + TX, butocarboxim + TX, butonate + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium arsenate + TX, calcium cyanide + TX, calcium polysulfide + TX, camphechlor + TX, captafol + TX, captan + TX, carbanolate + TX, carbendazim + TX, carbon disulfide + TX, carbon tetrachloride + TX, carbophenothion + TX, carboxin + TX, cartap hydrochloride + TX, CAS Number: 2049581-78-2 + TX, CAS Number: 2454319-63-0 + TX, CAS Number: 3052252-62-4 + TX, CAS Number: 3052252-63-5 + TX, CAS Number: 83-46-5 + TX, cevadine + TX, chinomethionat + TX, chloralose + TX, chlorbenside + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloroform + TX, chloroinconazide + TX, chloromebuform + TX, chloromethiuron + TX, chloroneb + TX, chlorophacinone + TX, chloropicrin + TX, chloropropylate + TX, chlorothalonil + TX, chlorphoxim + TX, chlorprazophos + TX, chlorthiophos + TX, chlozolinate + TX, cholecalciferol + TX, Chrysoperla carnea + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, cismethrin + TX, cis-resmethrin + TX, clocythrin + TX, closantel + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX, copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper sulfate + TX, coumachlor + TX, coumafuryl + TX, coumaphos + TX, coumatetralyl + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, coumithoate + TX, coumoxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, crotoxyphos + TX, crufomate + TX, cryolite + TX, Cryptolaemus montrouzieri + TX, CS 708 + TX, cuelure + TX, cufraneb + TX, cyanofenphos + TX, cyanophos + TX, cyanthoate + TX, cyazofamid + TX, cybutryne + TX, cyclethrin + TX, cyclobutrifluram + TX, Cydia pomonella GV + TX, cyflufenamid + TX, cymiazole + TX, cymoxanil + TX, cyproconazole + TX, cyprodinil + TX, cythioate + TX, cytokinins + TX, Dacnusa sibirica + TX, DAEP + TX, dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, debacarb + TX, decarbofuran + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S- methylsulfon + TX, diamidafos + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dicapthon + TX, dichlobentiazox + TX, dichlofenthion + TX, dichlofluanid + TX, dichlone + TX, dichlorophen + TX, dichlorvos + TX, dichlozoline + TX, dicliphos + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, dicresyl + TX, dicyclanil + TX, dicyclopentadiene + TX, dieldrin + TX, dienochlor + TX, diethofencarb + TX, 109921 | 83192 FF diethyl 5-methylpyrazol-3-yl phosphate + TX, diethyltoluamide + TX, difenacoum + TX, difenoconazole + TX, difethialone + TX, diflovidazin + TX, Diglyphus isaea + TX, dilor + TX, dimatif + TX, dimefluthrin + TX, dimefox + TX, dimetan + TX, dimethirimol + TX, dimethomorph + TX, dimethrin + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimethylvinphos + TX, dimetilan + TX, dimoxystrobin + TX, dinex + TX, dinex- diclexine + TX, diniconazole + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, dinosulfon + TX, dinoterbon + TX, diofenolan + TX, dioxabenzofos + TX, dioxathion + TX, diphacinone + TX, diphenyl sulfone + TX, dipymetitrone + TX, dipyrithione + TX, disparlure + TX, disulfiram + TX, dithianon + TX, dithicrofos + TX, DNOC + TX, dodec-8- en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, dodemorph + TX, dodicin + TX, dodine + TX, dofenapyn + TX, dominicalure + TX, doramectin + TX, DSP + TX, d-tetramethrin + TX, ecdysterone + TX, edifenphos + TX, EI 1642 + TX, EMPC + TX, Encarsia formosa + TX, endothal + TX, endothion + TX, enestroburin + TX, enoxastrobin + TX, EPBP + TX, epoxiconazole + TX, eprinomectin + TX, Eretmocerus eremicus + TX, ergocalciferol + TX, etaphos + TX, ethaboxam + TX, ethiofencarb + TX, ethirimol + TX, ethoate-methyl + TX, ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3- carboxylate (may be prepared from the methods described in WO 2020/056090) + TX, ethyl 1-[[4-[[2- (trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020/056090) + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]pyrazole-4-carboxylate + TX, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2- thienyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2018/158365) + TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, etridiazole + TX, etrimfos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol with nerolidol + TX, fenamidone + TX, fenaminosulf + TX, fenaminstrobin + TX, fenarimol + TX, fenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fenchlorphos + TX, feneptamidoquin (CAS Number: 2132414-04-9) + TX, fenethacarb + TX, fenfuram + TX, fenhexamid + TX, fenitrothion + TX, fenopyramid (CAS Number: 2344721-61-3) + TX, fenothiocarb + TX, fenoxacrim + TX, fenoxanil + TX, fenpiclonil + TX, fenpicoxamid + TX, fenpirithrin + TX, fenpropidin + TX, fenpropimorph + TX, fenpyrad + TX, fenpyrazamine + TX, fenpyroximate + TX, fenson + TX, fensulfothion + TX, fenthion + TX, fenthion-ethyl + TX, fentin + TX, fentrifanil + TX, ferbam + TX, ferimzone + TX, ferric phosphate + TX, flocoumafen + TX, florylpicoxamid + TX, fluazinam + TX, flubeneteram + TX, flubenzimine + TX, flucofuron + TX, flucycloxuron + TX, fludioxonil + TX, fluenetil + TX, flufenoxadiazam + TX, flufenoxystrobin + TX, fluindapyr + TX, flumetylsulforim + TX, flumorph + TX, fluopicolide + TX, fluopimomide + TX, fluopyram + TX, fluorbenside + TX, fluoroacetamide + TX, fluoroimide + TX, fluoxapiprolin + TX, fluoxastrobin + TX, fluoxytioconazole + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluquinconazole + TX, flusilazole + TX, flusulfamide + TX, flutianil + TX, flutolanil + TX, flutriafol + TX, fluxapyroxad + TX, FMC 1137 + TX, folpet + TX, formaldehyde + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, fosetyl-aluminium + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, frontalin + TX, fuberidazole + TX, furalaxyl + TX, furametpyr + TX, furathiocarb + TX, furethrin + TX, furfural + TX, gamma-HCH + TX, glyodin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure 109921 | 83192 FF III + TX, grandlure IV + TX, guazatine + TX, guazatine acetates + TX, halfenprox + TX, HCH + TX, hemel + TX, hempa + TX, HEOD + TX, heptachlor + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexaconazole + TX, hexadecyl cyclopropanecarboxylate + TX, hexalure + TX, hexamide + TX, HHDN + TX, Hippodamia convergens + TX, hydrargaphen + TX, hydrated lime + TX, hydrogen cyanide + TX, hymexazol + TX, hyquincarb + TX, imanin + TX, imazalil + TX, imibenconazole + TX, iminoctadine + TX, inpyrfluxam + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenphos + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidofos + TX, isazofos + TX, isobenzan + TX, isocarbophos + TX, isodrin + TX, isofenphos + TX, isofetamid + TX, isoflucypram + TX, isolane + TX, isoprothiolane + TX, isopyrazam + TX, isotianil + TX, isoxathion + TX, japonilure + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kadethrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kelevan + TX, kinetin + TX, kinoprene + TX, kresoxim-methyl + TX, lead arsenate + TX, Leptomastix dactylopii + TX, leptophos + TX, lindane + TX, lineatin + TX, lirimfos + TX, litlure + TX, looplure + TX, lvbenmixianan + TX, lythidathion + TX, Macrolophus caliginosus + TX, magnesium phosphide + TX, malonoben + TX, Mamestra brassicae NPV + TX, mancopper + TX, mancozeb + TX, mandestrobin + TX, mandipropamid + TX, maneb + TX, mazidox + TX, m-cumenyl methylcarbamate + TX, mecarbam + TX, mecarphon + TX, medlure + TX, mefentrifluconazole + TX, megatomoic acid + TX, menazon + TX, mepanipyrim + TX, meperfluthrin + TX, mephosfolan + TX, mepronil + TX, mercuric oxide + TX, mercurous chloride + TX, mesulfen + TX, mesulfenfos + TX, metalaxyl + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020/193387) + TX, methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2- methyl-phenoxy]-3-methoxy-prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1- yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2- enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds may be prepared from the methods described in WO2020/079111) + TX, methyl (Z)-3- methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methyl N-[[4-[1-(2,6-difluoro-4- isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2- methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, methylchloroform + TX, methylene chloride + TX, methylneodecanamide + TX, metiram + TX, metolcarb + TX, metomi-nostrobin + TX, metoxadiazone + TX, metrafenone + TX, metyltetraprole + TX, MGK 264 + TX, milbemycin oxime + TX, mipafox + TX, mirex + TX, monocrotophos + TX, morphothion + TX, morzid + TX, moxidectin + TX, 109921 | 83192 FF muscalure + TX, myclobutanil + TX, myclozoline + TX, Myrothecium verrucaria composition + TX, N-((1R)-1- benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017/153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8- fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017/153380) + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-(2- chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (THESE COMPOUNDS may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689) + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3- dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8- fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3- carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1- benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(E)-methoxyiminomethyl]-4- [5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide + TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole- 4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole- 4-carboxamide + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in WO 2016/202742) + TX, N'-[4-(4,5- dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1- methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2- propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2015/155075) + TX, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl- N-methyl-formamidine (this compound may be prepared from the methods described in IPCOM000249876D) + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N-[N- methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds may be prepared from the methods described in WO 2018/202428) + TX, N’-[4-(1-cyclopropyl-2,2,2-trifluoro- 1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2018/228896) + TX, nabam + TX, naftalofos + TX, naled + TX, naphthalene + TX, NC-170 + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nerolidol + TX, N-ethyl- 2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-N’-[5- methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide-olamine + TX, nicotine + TX, nicotine sulfate + TX, nifluridide + TX, nikkomycins + TX, N-isopropyl-N’-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl- ethyl)phenyl]-N-methyl-formamidine + TX, nithiazine + TX, nitrapyrin + TX, nitrilacarb + TX, nitrilacarb 1:1 109921 | 83192 FF zinc chloride complex + TX, nitrothal-isopropyl + TX, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]benzamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX, norbormide + TX, nuarimol + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, ofurace + TX, oleic acid + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, orysastrobin + TX, ostramone + TX, oxadixyl + TX, oxamate + TX, oxathiapiprolin + TX, oxine-copper + TX, oxolinic acid + TX, oxycarboxin + TX, oxydeprofos + TX, oxydisulfoton + TX, oxytetracycline + TX, paclobutrazole + TX, Paecilomyces fumosoroseus + TX, para-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, pefurazoate + TX, penconazole + TX, pencycuron + TX, penflufen + TX, penfluron + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, penthiopyrad + TX, permethrin + TX, PH 60-38 + TX, phenamacril + TX, phenkapton + TX, phosacetim + TX, phosalone + TX, phosdiphen + TX, phosfolan + TX, phosglycin + TX, phosnichlor + TX, phosphamidon + TX, phosphine + TX, phosphorus + TX, phoxim-methyl + TX, phthalide + TX, Phytoseiulus persimilis + TX, picarbutrazox + TX, picaridin + TX, picoxystrobin + TX, pindone + TX, piperazine + TX, piperonyl butoxide + TX, piprotal + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, polychloroterpenes + TX, polynactins + TX, polyoxins + TX, potassium arsenite + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, potassium thiocyanate + TX, pp'- DDT + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, probenazole + TX, prochloraz + TX, proclonol + TX, procymidone + TX, profluthrin + TX, promacyl + TX, promecarb + TX, propamocarb + TX, propiconazole + TX, propineb + TX, propoxur + TX, propyl isomer + TX, proquinazid + TX, prothidathion + TX, prothioconazole + TX, prothiofos + TX, prothoate + TX, pydiflumetofen + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, pyrapropoyne + TX, pyraziflumid + TX, pyrazophos + TX, pyresmethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyribencarb + TX, pyridachlometyl + TX, pyridaphenthion + TX, pyridin-4-amine + TX, pyrifenox + TX, pyrimethanil + TX, pyrimitate + TX, pyrimorph + TX, pyrinuron + TX, pyriofenone + TX, pyrisoxazole + TX, pyroquilon + TX, quassia + TX, quinalphos + TX, quinalphos-methyl + TX, quinoclamine + TX, quinofumelin + TX, quinonamid + TX, quinothion + TX, quinoxyfen + TX, quintiofos + TX, quintozene + TX, R-1492 + TX, rafoxanide + TX, resmethrin + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, R metalaxyl + TX, rotenone + TX, ryania + TX, ryanodine + TX, S421 + TX, sabadilla + TX, schradan + TX, scilliroside + TX, seboctylamine + TX, sebufos + TX, sedaxane + TX, selamectin + TX, sesamex + TX, sesasmolin + TX, SI-0009 + TX, siglure + TX, simazine + TX, simeconazole + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium fluoroacetate + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium tetrathiocarbonate + TX, sodium thiocyanate + TX, sophamide + TX, sordidin + TX, spiroxamine + TX, SSI-121 + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfoxide + TX, sulfur + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tau-fluvalinate + TX, 109921 | 83192 FF tazimcarb + TX, TDE + TX, tebuconazole + TX, tebufloquin + TX, tebupirimfos + TX, tecloftalam + TX, temephos + TX, tepa + TX, TEPP + TX, terallethrin + TX, terbam + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5- yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, tetrachloroethane + TX, tetrachlorothiophene + TX, tetraconazole + TX, tetradec-11-en-1-yl acetate + TX, tetradifon + TX, tetramethylfluthrin + TX, tetrasul + TX, thallium sulfate + TX, thiabendazole + TX, thiafenox + TX, thiapronil + TX, thicrofos + TX, thifluzamide + TX, thiocarboxime + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodiazole copper + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiophanate-methyl + TX, thioquinox + TX, thiosultap + TX, thiosultap-sodium + TX, thiotepa + TX, thiram + TX, thuringiensin + TX, tiadinil + TX, tolclofos-methyl + TX, tolprocarb + TX, tolylfluanid + TX, tralomethrin + TX, transpermethrin + TX, tretamine + TX, triadimefon + TX, triadimenol + TX, triamiphos + TX, triarathene + TX, triazamate + TX, triazophos + TX, triazoxide + TX, triazuron + TX, tributyltin oxide + TX, trichlormetaphos-3 + TX, trichloronat + TX, Trichogramma spp. + TX, triclopyricarb + TX, tricyclazole + TX, tridemorph + TX, trifenmorph + TX, trifenofos + TX, trifloxystrobin + TX, triflumizole + TX, triforine + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, trinactin + TX, trinexapac + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, triprene + TX, triticonazole + TX, trunc-call + TX, Typhlodromus occidentalis + TX, uredepa + TX, validamycin + TX, valifenalate + TX, vamidothion + TX, vaniliprole + TX, veratridine + TX, veratrine + TX, verbutin + TX, Verticillium lecanii + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenols + TX, zeatin + TX, zetamethrin + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, zinc thiazole + TX, zineb + TX, ziram + TX, zolaprofos + TX, zoxamide + TX, α- (1, 1- dimethylethyl) - α- [4'- (trifluoromethoxy) [1, 1'- biphenyl] - 4- yl] -5- pyrimidinemethanol + TX; Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®) in particular strain CNMC 1-1582 (e.g. VOTIVO® from BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus licheniformis strain HB-2 (Biostart™ formerly Rhizoboost®) + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain QST 2808 (Sonata®, Ballad Plus®) + TX, Bacillus sphaericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, 109921 | 83192 FF Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP ®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis tenebrionis (Novodor®, BtBooster) + TX, Bacillus thuringiensis var. aizawai (XenTari®, DiPel®) + TX, bacteria spp. (GROWMEND®, GROWSWEET®, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®, Bakflor®) + TX, Beauveria bassiana (Beaugenic®, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES®, Mycotrol O®, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz®, Schweizer Beauveria®, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea davisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova- Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium chlorocephalum + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®, Madex®, Madex® Plus, Madex Max, Carpovirusine® + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isaria fumosorosea (previously known as Paecilomyces fumosoroseus strain, PFR-97®, PreFeRal®) + TX, 109921 | 83192 FF Isoflavone formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii (Mycotal®) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metarhizium anisopliae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus in particular strain A3-5 (Accession No. NRRL 30548) + TX, Mycorrhizae spp. (AMykor®, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta/ChemChina); + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal®, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp. + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor (SARRITOR®) + TX, Sclerotinia minor + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®, Spexit®) + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma gamsii (Tenet®) + TX, 109921 | 83192 FF Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P®, PlantShield HC®, RootShield®, Trianum-G® + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp. + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus + TX; AGNIQUE® MMF + TX, azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X® e.g. AZATIN XL from Certis, US) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, BugOil® + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, essentials oils of Labiatae (Botania®) + TX, extract of neem oil (Trilogy®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, garlic + TX, Glycinebetaine (Greenstim®) + TX, kaolin (Screen®) + TX, lemongrass oil (GreenMatch®) + TX, Melaleuca alternifolia extract (also called tea tree oil) (Timorex Gold®) + TX, mixture of clove pepermint garlic oil and mint (Soil Shot®) + TX, mixture of clove rosemary and peppermint extract (EF 400®) + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®) + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pine oil (Retenol®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia®, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, storage glucam of brown algae (Laminarin®) + TX, thyme oil + TX; (E,Z)-7,9-Dodecadien-1-yl acetate + TX, (E,Z,Z)-3,8,11 Tetradecatrienyl acetate + TX, (Z,Z,E)- 7,11,13-Hexadecatrienal + TX, 2-Methyl-1-butanol + TX, Biolure® + TX, blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Calcium acetate + TX, Check-Mate® + TX, Codling Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Lavandulyl senecioate + TX, Leafroller pheromone (3M MEC – LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone (Isomate-P®) + TX, Scenturion® + TX, Starbar Premium Fly Bait®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX; Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus (Amblyline®, Spical®) + TX, Amblyseius cucumeris (Thripex®, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, 109921 | 83192 FF Amblyseius swirskii (Bugline swirskii®, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline®, Aphiline®), + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Aphelinus- System®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®, Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®, Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus®, Digline®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max®, Encarline®, En-Strip®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Enermix®, Ercal®, Eretline e®, Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar®, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Feltiline®) + TX, Feltiella acarisuga (Spidend®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis bacteriophora (NemaShield HB®, Nemaseek®, Terranem-Nam®, Terranem®, Larvanem®, B-Green®, NemAttack ®, Nematop®) + TX, Heterorhabditis megidis (Nemasys H®, BioNem H®, Exhibitline hm®, Larvanem-M®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System®, Entomite-A®) + TX, Hypoaspis miles (Hypoline m®, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N®, Macroline c®, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug®, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I®, Oriline i®) + TX, Orius laevigatus (Thripor-L®, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, 109921 | 83192 FF Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex®, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C®, Millenium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®) + TX, Steinernema feltiae (NemaShield®, Nemasys F®, BioNem F®, Steinernema-System®, NemAttack®, Nemaplus®, Exhibitline sf®, Scia-rid®, Entonem®) + TX, Steinernema kraussei (Nemasys L®, BioNem L®, Exhibitline srb®) + TX, Steinernema riobrave (BioVector®, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho- Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta traps (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct®, Ni-HIBIT Gold CST®) + TX, fatty acids derived from a natural by-product of extra virgin olive oil (FLIPPER®) + TX, Ferri-phosphate (Ferramol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium iodide + potassiumthiocyanate (Enzicur®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, Spider venom + TX, Sticky traps (Trapline YF®, Rebell Amarillo®) + TX, SuffOil-X® + TX, Traps (Takitrapline y + b®) + TX, vadescana (CAS Number: 2643947-26-4) + TX, Zenox® + TX; Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX, Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No.50185 (CARTISSA® from BASF, EPA Reg. No. 71840-19) + TX, Bacillus subtilis CX-9060 from Certis USA LLC, Bacillus sp., in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S. Patent No.7,094,592 + TX, Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661 and described in U.S. Patent No.6,060,051, available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US) + TX, Paenibacillus polymyxa, in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Paenibacillus 109921 | 83192 FF sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX, Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX, Saccharomyces cerevisiae, in particular strains CNCM No.1-3936, CNCM No.1-3937, CNCM No.1-3938 or CNCM No.1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR + TX; Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA) + TX, Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREEN™ from University of Pretoria) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768, WO 2014/028521) (STARGUS® from Marrone Bio Innovations) + TX, Bacillus amyloliquefaciens strain FZB42, Accession No. DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No.7,094,592) + TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX, Bacillus licheniformis, in particular strain SB3086, having Accession No. ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAF™ from Novozymes) + TX, Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX, Bacillus mycoides, isolate, having Accession No. B-30890 (available as BMJ TGAI® or WG and LifeGard™ from Certis USA LLC) + TX, Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX, Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No.6,245,551) + TX, Bacillus subtilis CX-9060 from Certis USA LLC + TX, Bacillus subtilis IAB/BS03 (AVIV™ from STK Bio- Ag Technologies, PORTENTO® from Idai Nature) + TX, Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX, Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX, Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S. Patent No.5,061,495 + TX, Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX, Paenibacillus polymyxa ssp. plantarum (WO 2016/020371) from BASF SE + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or 109921 | 83192 FF Accession No. NRRL B-67129, WO 2016/154297 + TX, Pseudomonas chlororaphis strain AFS009, having Accession No. NRRL B-50897, WO 2017/019448 (e.g., HOWLER™ and ZIO® from AgBiome Innovations, US) + TX, Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert) + TX, Pseudomonas fluorescens strain A506 (e.g. BLIGHTBAN® A506 by NuFarm) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf. Crop Protection 2006, 25, 468-475) + TX, Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO- IRON® and ACTINOVATE® from Novozymes) + TX; Trichoderma atroviride strain T11 (IMI352941/ CECT20498) + TX, Ampelomyces quisqualis strain AQ10, having Accession No. CNCM 1-807 (e.g., AQ 10® by IntrachemBio Italia) + TX, Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD® from Syngenta/ChemChina) + TX, Aureobasidium pullulans, in particular blastospores of strain DSM 14941 + TX, Aureobasidium pullulans, in particular blastospores of strain DSM14940 + TX, Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH) + TX, Chaetomium cupreum (Accession No. CABI 353812) (e.g. BIOKUPRUM™ by AgriLife) + TX, Chaetomium globosum (available as RIVADIOM® by Rivale) + TX, Cladosporium cladosporioides, strain H39, having Accession No. CBS122244, US 2010/0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM9660, e.g. Contans ® from Bayer CropScience Biologics GmbH) + TX, Cryptococcus flavescens, strain 3C (NRRL Y-50378), + TX, Dactylaria candida, Dilophosphora alopecuri (available as TWIST FUNGUS®), Fusarium oxysporum, strain Fo47 (available as FUSACLEAN® by Natural Plant Protection) + TX, Gliocladium catenulatum (Synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g. Prestop ® by Lallemand) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea) strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain ’IK726’, Australasian Plant Pathol. 2007,36(2):95-101) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue A.G. (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 2003, 83(3): 519-524) + TX, Metschnikowia fructicola, in particular strain NRRL Y-30752 + TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, WO 2015/067800) from BASF SE + TX, mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), having Accession No. CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080, having Accession No. IMI 392151 (e.g., BIO-TAM™ from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM 109921 | 83192 FF No.1-3936, CNCM No.1-3937, CNCM No.1-3938, CNCM No.1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR + TX, Saccharomyces cerevisiae, in particular strain LASO2 (from Agro-Levures et Dérivés) + TX, Simplicillium lanosoniveum + TX, strain T34 (e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro + TX, strain WRL-076 (NRRL Y-30842), U.S. Patent No.7,579,183 + TX, Talaromyces flavus, strain V117b + TX, Trichoderma asperelloides JM41R (Accession No. NRRL B-50759) (TRICHO PLUS® from BASF SE) + TX, Trichoderma asperellum, in particular strain SKT-1, having Accession No. FERM P-16510 (e.g. ECO-HOPE® from Kumiai Chemical Industry) + TX, Trichoderma asperellum, in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride strain 77B (T77 from Andermatt Biocontrol) + TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040) + TX, Trichoderma atroviride strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX, Trichoderma atroviride strain LU132 (e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain NMI no. V08/002388 + TX, Trichoderma atroviride strain NMI no. V08/002389 + TX, Trichoderma atroviride strain NMI no. V08/002390 + TX, Trichoderma atroviride strain no. V08/002387 + TX, Trichoderma atroviride strain SKT-1 (FERM P-16510), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-2 (FERM P-16511), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-3 (FERM P-17021), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089, WO 2009/116106 and U.S. Patent No.8,431,120 (from Bi- PA)) + TX, Trichoderma atroviride,strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma harmatum + TX, Trichoderma harmatum, having Accession No. ATCC 28012 + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US) + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro), + TX, Trichoderma harzianum strain DB 103 (available as T- GRO® 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g. Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g. Root-Pro by Mycontrol) + TX, Trichoderma polysporum strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden) + TX, Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX, Trichoderma virens (also known as Gliocladium virens) in particular strain GL-21 (e.g. SoilGard by Certis, US) + TX, Trichoderma virens strain G- 41, formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1(e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No. NM 99/06216 (e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; 109921 | 83192 FF a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX, Azospirillum lipoferum (e.g., VERTEX-IF™ from TerraMax, Inc.) + TX, Azotobacter chroococcum, in particular strain H23 + TX, Azotobacter vinelandii, in particular strain ATCC 12837 + TX, Bacillus amyloliquefaciens BS27 (Accession No. NRRL B-5015) + TX, Bacillus amyloliquefaciens in particular strain FZB42 (e.g. RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens in particular strain IN937a + TX, Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection) + TX, Bacillus amyloliquefaciens SB3281 (ATCC # PTA-7542, WO 2017/205258) + TX, Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® from Novozymes) + TX, Bacillus cereus family member EE128 (NRRL No. B-50917) + TX, Bacillus cereus family member EE349 (NRRL No. B-50928) + TX, Bacillus cereus in particular strain BP01 (ATCC 55675, e.g. MEPICHLOR® from Arysta Lifescience, US) + TX, Bacillus mycoides BT155 (NRRL No. B-50921) + TX, Bacillus mycoides BT46-3 (NRRL No. B-50922) + TX, Bacillus mycoides EE118 (NRRL No. B-50918) + TX, Bacillus mycoides EE141 (NRRL No. B-50916) + TX, Bacillus pumilus in particular strain GB34 (e.g. YIELD SHIELD® from Bayer Crop Science, DE), + TX, Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B-50421 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g. SUBTILEX® from BASF SE) + TX, Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE) + TX, Bacillus tequilensis in particular strain NII-0943 + TX, Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7 + TX, Bradyrhizobium japonicum (e.g. OPTIMIZE® from Novozymes) + TX, Delftia acidovorans in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds) + TX, Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708), + TX, Sinorhizobium meliloti strain NRG- 185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g. CROPAID® from Cropaid Ltd UK) + TX; Myrothecium verrucaria strain AARC-0255 (e.g. DiTera™ from Valent Biosciences) + TX, Penicillium bilaii strain ATCC 22348 (e.g. JumpStart® from Acceleron BioAg) + TX, Penicillium bilaii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (previously known as Paecilomyces lilacinus) strain 251 (AGAL 89/030550, e.g. BioAct from Bayer CropScience Biologics GmbH) + TX, Pythium oligandrum strain DV74 + TX, Pythium oligandrum strain M1 (ATCC 38472 e.g. Polyversum from Bioprepraty, CZ) + TX, Rhizopogon 109921 | 83192 FF amylopogon (Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Rhizopogon fulvigleba (e.g. Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Talaromyces flavus strain V117b + TX, Trichoderma asperellum strain (Eco-T from Plant Health Products, ZA) + TX, Trichoderma asperellum strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride in particular strain no. V08/002387 + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain no. NMI No. V08/002388 + TX, Trichoderma atroviride strain no. NMI No. V08/002389 + TX, Trichoderma atroviride strain no. NMI No. V08/002390 + TX, Trichoderma atroviride strain SC1 (described in WO2009/116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g. SoilGard® from Certis, USA) + TX, Trichoderma viride strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g. Dutch Trig from Tree Care Innovations) + TX; Agrobacterium radiobacter strain K84 (Galltrol from AgBiochem Inc.), + TX, Bacillus amyloliquefaciens in particular strain PTS-4838 (e.g. AVEO from Valent Biosciences, US), + TX, Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC), + TX, Bacillus sphaericus in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX® from Valent BioSciences, US), + TX, Bacillus thuringiensis israelensis strain BMP 144 (e.g. AQUABAC® by Becker Microbial Products IL) + TX, Bacillus thuringiensis subsp. aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX, Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. DIPEL® ES from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain PB 54 + TX, Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX, Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var. japonensis strain Buibui + TX, Bacillus thuringiensis var. kurstaki strain EVB-113- 19 (e.g., BIOPROTEC® from AEF Global) + TX, Brevibacillus laterosporus + TX, Burkholderia spp. in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319, WO 2011/106491 and WO 2013/032693, e.g. MBI206 TGAI and ZELTO® from Marrone Bio Innovations), + TX, Chromobacterium subtsugae in particular strain PRAA4-1T (e.g. MBI- 109921 | 83192 FF 203, e.g. GRANDEVO® from Marrone Bio Innovations) + TX, Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX, Paenibacillus popilliae (formerly Bacillus popilliae, e.g. MILKY SPORE POWDER™ or MILKY SPORE GRANULAR™ from St. Gabriel Laboratories) + TX, Serratia entomophila (e.g. INVADE® by Wrightson Seeds) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708) + TX, Trichoderma asperellum (TRICHODERMAX from Novozymes) + TX, Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from MosquitoMate) + TX; Beauveria bassiana strain ATCC 74040 (e.g. NATURALIS® from Intrachem Bio Italia) + TX, Beauveria bassiana strain ATP02 (Accession No. DSM 24665), Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (Accession No. ATCC74250, e.g. BOTANIGUARD® ES and MYCONTROL- O® from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017/066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX, Zoophtora radicans + TX; Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, Spodoptera exigua (beet armyworm) mNPV + TX, Spodoptera frugiperda (fall armyworm) mNPV + TX, Spodoptera littoralis (African cotton leafworm) NPV + TX; Burkholderia spp. in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, LactoBacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp. in particular Rhizobium trifolii + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp. + TX, Agrobacterium spp. + TX, Azorhizobium caulinodans + TX, Azospirillum spp. + TX, Azotobacter spp. + TX, Bradyrhizobium spp. + TX, Gigaspora monosporum + TX; Allium sativum (NEMGUARD from Eco-Spray, BRALIC from ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, Biokeeper WP + TX, Brassicaceae extract in particular oilseed rape powder or mustard powder + TX, Cassia nigricans + TX, Celastrus angulatus + TX, Chenopodium anthelminticum + TX, Chenopodium quinoa saponin extract from quinoa seeds (e.g. Heads Up® (Saponins of Quinoa) from Heads Up plant Protectants, CA) + TX, Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD from STK) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (FRACTURE® from FMC) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (PROBLAD® from Certis EU) + TX, Pyrethrins + TX, Quassia amara + TX, Quercus + TX, Quillaja extract (QL AGRI 35 from BASF) + TX, REGALIA MAXX from Marrone Bio) + TX, Requiem™ Insecticide + TX, Reynoutria sachalinensis extract (REGALLIA + TX, ryania/ryanodine + TX, Symphytum officinale + TX, Tanacetum vulgare + TX, Thymol + TX, Thymol mixed with Geraniol (CEDROZ from Eden Research) + TX, Thymol mixed with Geraniol and Eugenol (MEVALONE from Eden Research) + TX, Triact 70 + TX, TriCon + TX, Tropaeulum majus + TX, Urtica dioica + TX, Veratrin + TX, Viscum album + TX; 109921 | 83192 FF mercuric oxide + TX, octhilinone + TX, thiophanate-methyl + TX; MGK 264 + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-isovalerylindan-1,3-dione + TX, 4- (quinoxalin-2-ylamino)benzenesulfonamide + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, alpha-bromadiolone + TX, alpha-chlorohydrin + TX, aluminium phosphide + TX, anthraquinone + TX, antu + TX, arsenous oxide + TX, barium carbonate + TX, benoxacor + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, calcium cyanide + TX, chloralose + TX, chlorophacinone + TX, cholecalciferol + TX, cloquintocet (including cloquintocet-mexyl) + TX, copper naphthenate + TX, copper oxychloride + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, cyprosulfamide + TX, diazinon + TX, dichlormid + TX, dicyclopentadiene + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, farnesol + TX, farnesol with nerolidol + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluxofenim + TX, furilazole + TX, gamma-HCH + TX, guazatine + TX, guazatine acetates + TX, HCH + TX, hydrogen cyanide + TX, imanin + TX, iodomethane + TX, isoxadifen (including isoxadifen-ethyl) + TX, lindane + TX, magnesium phosphide + TX, MB-599 + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX, methiocarb + TX, methyl bromide + TX, nerolidol + TX, norbormide + TX, petroleum oils + TX, phosacetim + TX, phosphine + TX, phosphorus + TX, pindone + TX, piperonyl butoxide + TX, piprotal + TX, potassium arsenite + TX, probenazole + TX, propyl isomer + TX, pyridin-4-amine + TX, pyrinuron + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, S421 + TX, scilliroside + TX, sesamex + TX, sesasmolin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thiram + TX, trimethacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, ziram + TX. [0302] The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html. [0303] Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number. 109921 | 83192 FF [0304] The active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight. [0305] The compounds and mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a compound or mixture respectively as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body. [0306] The mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-30 and Tables B-1 to B-5, and Table P, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture com-posed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequen-tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention. [0307] The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, micro-emulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents. [0308] The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface- active substances or combinations thereof. 109921 | 83192 FF [0309] The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated. [0310] The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethyl-formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. [0311] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances. [0312] A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, 109921 | 83192 FF salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981). [0313] Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers. [0314] The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010. [0315] The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formula-tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations. [0316] The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha. [0317] Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates: ^ active ingredient: 1 to 95 %, preferably 60 to 90 % ^ surface-active agent: 1 to 30 %, preferably 5 to 20 % ^ liquid carrier: 1 to 80 %, preferably 1 to 35 % 109921 | 83192 FF Dusts: ^ active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % ^ solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: ^ active ingredient: 5 to 75 %, preferably 10 to 50 % ^ water: 94 to 24 %, preferably 88 to 30 % ^ surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders: ^ active ingredient: 0.5 to 90 %, preferably 1 to 80 % ^ surface-active agent: 0.5 to 20 %, preferably 1 to 15 % ^ solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: ^ active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % ^ solid carrier: 99.5 to 70 %, preferably 97 to 85 % [0318] Formulation types include an emulsifiable concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. A short definition of formulation types may be found in the OECD Guidance for Industry Data Submissions on Plant Protection Products and their Active Substances (Revision 2 May 2005), Appendix 2. [0319] The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use. [0320] Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations. [0321] The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, 109921 | 83192 FF rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides. [0322] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention. [0323] The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha. [0324] A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredi-ent can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field. [0325] The compounds of formula (I) of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds. [0326] The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds. [0327] The present invention also comprises seeds coated or treated with or containing a compound of formula (I). The term "coated or treated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the 109921 | 83192 FF ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I). [0328] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds. [0329] The compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m2. The greater efficacy can be observed by an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability). [0330] In each aspect and embodiment of the invention, "consisting essentially" and inflections thereof are a preferred embodiment of "comprising" and its inflections, and "consisting of" and inflections thereof are a preferred embodiment of "consisting essentially of" and its inflections. [0331] The disclosure in the present application makes available each and every combination of embodiments disclosed herein. [0332] It should be noted that the disclosure herein in respect of a compound of formula (I) applies equally in respect of a compound of each of formulae (I*), (I’a), Tables A-1 to A-30 and Tables B-1 to B-5. EXAMPLES Formulation Examples [0333] The following Examples further illustrate, but do not limit, the invention. Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - 109921 | 83192 FF [0334] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration. Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - 20 % [0335] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment. Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % [0336] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c) Active ingredients 5 % 6 % 4 % Talcum 95 % - - Kaolin - 94 % - mineral filler - - 96 % [0337] Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. Extruded granules 109921 | 83192 FF Active ingredients 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % Kaolin 82 % [0338] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. Coated granules Active ingredients 8 % polyethylene glycol (mol. wt.200) 3 % Kaolin 89 % [0339] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 % [0340] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 109921 | 83192 FF 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 % [0341] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Slow Release Capsule Suspension [0342] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose. Preparatory Examples [0343] Free radicals represent methyl groups.1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion [M+H]+ or [M-H]-. Method 1: [0344] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 1.5 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 1.0 min, 100% B isocratic for 0.2min, 100-10% B in 0.05min, 10% B isocratic for 0.05 min. 109921 | 83192 FF Method 2: [0345] Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode- array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60°C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1% formic acid, B= Acetonitrile + 0.1% formic acid, gradient: 0-100% B in 3.0 min; Flow (ml/min) 0.75. Method 3: [0346] Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector. Column: Acquity UPLC HSS T3 C18, 1.8 µm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.-0.2 min 10-50% B; 0.2-0.6 min 50-100% B; 0.6-1.3 min 100% B; 1.3-1.4 min 100-10% B; 1.4-1.6 min 10% B; Flow (mL/min) 0.6. Method 4: [0347] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 3.0 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 2.5 min, 100% B isocratic for 0.3 min.
109921 | 83192 FF Example E1: Preparation of N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-2-oxo-6- (trifluoromethyl)-3H-benzimidazole-4-carboxamide (P1) Step 1: Preparation of N-cyclopropyl-2-nitro-5-(trifluoromethyl)aniline (I-1) [0348] To a solution of 2-fluoro-1-nitro-4-(trifluoromethyl)benzene (0.5 g, 2.39 mmol) in acetonitrile (15.0 mL) was added dipotassium;carbonate (0.662 g, 4.78 mmol) and cyclopropanamine (0.15 g, 2.63 mmol) at room temperature and stirred at 80°C for 16 hours. The reaction mass was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated to get the title compound, which was used in the following step without purification. [0349] 1H NMR (400 MHz, CDCl3) δ ppm 8.26 (d, 1H), 8.13 (br s, 1H), 7.58 (s, 1H), 6.91 (dd, 1H), 2.59-2.67 (m, 1H), 0.92-1.05 (m, 2H), 0.64-0.76 (m, 2H). Step 2: Preparation of [2-(cyclopropylamino)-4-(trifluoromethyl)phenyl]ammonium;chloride (I-2) (I-2) [0350] To a solution of N-cyclopropyl-2-nitro-5-(trifluoromethyl)aniline (synthesis described hereabove) (2.0 g, 8.1 mmol) in ethyl acetate (20 mL) was added 10% palladium on carbon (0.17 g) under nitrogen atmosphere. The reaction mixture was stirred under hydrogen balloon atmosphere at room temperature for 8 hours. Reaction 109921 | 83192 FF mass was filtered through a layer of celite bed. The filtrate was treated with 4M HCl in ethyl acetate, the resulting suspension was filtered, and the residue was dried to get the title compound. [0351] 1H NMR (400 MHz, DMSO-d6) δ ppm 7.14-7.20 (m, 2H), 6.95-7.04 (m, 1H), 2.48-2.49 (m, 1H), 0.79 (dd, 2H), 0.45-0.51 (m, 2H). Step 3: Preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-benzimidazol-2-one (I-3) [0352] To a suspension of [2-(cyclopropylamino)-4-(trifluoromethyl)phenyl]ammonium;chloride (preparation described above) (1.0 g, 3.6 mmol, 90 mass%) in ethyl acetate (30 mL) was added N,N-diethylethanamine (1.9 g, 18 mmol) at 0°C, followed by bis(trichloromethyl) carbonate (0.54 g, 1.8 mmol) and the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by combiflash chromatography (ethyl acetate/hexane) to afford 3-cyclopropyl-5-(trifluoromethyl)-1H-benzimidazol-2-one. [0353] LCMS (method 3): retention time 1.02 min, m/z 243 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 11.21 (s, 1H), 7.35-7.37 (m, 2H), 7.12 (d, 1H), 2.90 (dt, 1H), 0.99-1.10 (m, 2H), 0.84-0.94 (m, 2H). Step 4: Preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-benzimidazol-2-one (I-4) (I-4) [0354] To a solution of 3-cyclopropyl-5-(trifluoromethyl)-1H-benzimidazol-2-one (preparation described above) (1.5 g, 6.2 mmol) in acetonitrile (15 mL) was added N-chloro succinimide (4.4 g, 25 mmol) at room temperature. The reaction mixture was stirred at room temperature for 27 hours, after what it was poured into sodium meta bisulfate solution (30 mL). The resulting suspension was filtered, the residue was washed with plenty of water, and dried to get the title compound. [0355] LCMS (method 3): retention time 1.09 min, m/z 321/323 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 8.83 (br s, 1H), 7.52 (s, 1H), 7.38 (s, 1H), 2.94 (dt, 1H), 1.17-1.23 (m, 2H), 1.02-1.13 (m, 2H). 109921 | 83192 FF Step 5: Preparation of methyl 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylate (I-5) (I-5) [0356] A 100 mL autoclave vessel was charged with 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H- benzimidazol-2-one (1.5 g, 4.7 mmol), N,N-diethylethanamine (4.7 mmol), methanol (38 mL), and Pd(dppf)Cl2 (0.47 mmol). The vessel was closed and flushed three times with nitrogen gas, then carbon monoxide was added under a pressure of 10 bars. The reaction mass was heated to 80°C. After 6 hours, the reaction mass was cooled to 25°C, the pressure was released and the apparatus was flushed with nitrogen. The reaction mixture was filtered through a path of celite and the filtrate was concentrated under reduced pressure to yield the crude title compound, which was used without purification in following step. [0357] LCMS (method 4): retention time 1.46 min, m/z 301 [M+H]+. Step 6: Preparation of 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) [0358] To a solution of methyl 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylate (preparation described above) (2.0 g, 2.3 mmol, 35 mass%) in methanol (20 mL) and water (10 mL) was added lithium hydroxide (0.28 g, 12 mmol) at room temperature. The reaction mixture was stirred at room temperature for 3 hours, then concentrated and the residue was acidified with 2N HCl and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and evaporated to get title compound. [0359] LCMS (method 3): retention time 0.99 min, m/z 287 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 11.14 (s, 1H), 7.76 (s, 1H), 7.56 (s, 1H), 2.94 (dt, 1H), 1.01-1.12 (m, 2H), 0.85-0.98 (m, 2H). 109921 | 83192 FF Step 7: Preparation of N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-2-oxo-6- (trifluoromethyl)-3H-benzimidazole-4-carboxamide (P1) [0360] To a mixture of 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (preparation described above) (0.23 g, 0.602 mmol, 75 mass%) and 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1- yl]pyridine-3-carbonitrile (0.142 g, 0.662 mmol) in acetonitrile (4.6 mL) was added 1-propanephosphonic acid cyclic anhydride in ethyl acetate (T3P®, 50 mass%) (0.498 g, 0.783 mmol) followed by N,N- diisopropylethylamine (0.318 g,2.41 mmol) at 0°C. The reaction mixture was stirred at room temperature for 6 hours. The reaction mass was then diluted with ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by combiflash chromatography (ethyl acetate/hexane) to afford the title compound. [0361] LCMS (method 3): retention time 1.05 min, m/z 483 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 11.67 (br s, 1H), 8.92 (d, 1H), 8.69 (br d, 1H), 8.24-8.32 (m, 2H), 7.99 (s, 1H), 7.56 (s, 1H), 7.26 (s, 1H), 6.16 (t, 1H), 2.51 (dt, 1H), 1.82 (d, 3H), 1.01-1.18 (m, 2H), 0.85-0.96 (m, 1H), 0.68-0.78 (m, 1H). Example E2: Preparation of N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl- 6-(difluoromethoxy)-2-oxo)-3H-benzimidazole-4-carboxamide (P30) [0362] To a mixture of 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I-12) (51.2 mg, 0.18 mmol, 1 equiv.) and [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2648588-51-4, prepared as described in WO 21/105091) (0.198 mmol, 1.1 equiv.) in DMA (0.75 mL) were added N,N-diisopropylethylamine (0.54 mmol, 3 equiv.), followed by a solution of HATU (0.198 mmol, 1.1 equiv.) in DMA (0.75 mL). The reaction mixture was stirred at RT overnight, quenched with MeOH (1 mL), 109921 | 83192 FF then submitted to reversed phase preparative HPLC (acetonitrile in water) to afford N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-6-(difluoromethoxy)-2-oxo)-3H- benzimidazole-4-carboxamide (P30) as a solid. [0363] LCMS (method 2): retention time 1.41 min, m/z 501 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.86 (m, 2H), 1.03 (m, 2H), 1.60 (br d, 3H), 2.34 (s, 3H), 2.85 (m, 1H), 6.03 (quint, 1H), 7.14 (s, 1H), 7.19 (t, J=74.3Hz, 1H), 7.46 (s, 1H), 8.64 (s, 1H), 9.24 (br s, 1H), 10.55 (br s, 1H). [0364] Similarly, N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-2-oxo- 6-(trifluoromethyl))-3H-benzimidazole-4-carboxamide (compound P11) was prepared from 1-cyclopropyl-2- oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) and [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5- methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-24, prepared as described below) by following above protocol in analogy. LCMS (method 2): retention time 1.38 min, m/z 551/553 [M+H]+. [0365] Similarly, N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]-1- cyclopropyl-2-oxo-6-(trifluoromethyl))-3H-benzimidazole-4-carboxamide (compound P9) was prepared from 1- cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) and [(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2694010-05-2, prepared in analogy to descriptions found for example in WO 21/224323) by following above protocol in analogy. LCMS (method 2): retention time 1.40 min, m/z 542 [M+H]+. [0366] Similarly, N-[(1S)-1-[2-(5-carbamoylpyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-2-oxo-6- (trifluoromethyl))-3H-benzimidazole-4-carboxamide (compound P20) was prepared from 1-cyclopropyl-2-oxo- 6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) and [(1S)-1-[2-(5-carbamoylpyrazin-2-yl)-1,2,4- triazol-3-yl]ethyl]ammonium chloride (CAS 3024825-20-2, prepared as described in WO 23/247360) by following above protocol in analogy. LCMS (method 2): retention time 1.16 min, m/z 502 [M+H]+. [0367] Similarly, 1-cyclopropyl-6-(difluoromethoxy)-N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4- triazol-3-yl]ethyl]-2-oxo)-3H-benzimidazole-4-carboxamide (compound P25) was prepared from 1-cyclopropyl- 6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I-12) and [(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5- methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-25) by following above protocol in analogy. LCMS (method 2): retention time 1.16 min, m/z 489 [M+H]+. [0368] Similarly, N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-6- (difluoromethoxy)-2-oxo)-3H-benzimidazole-4-carboxamide (compound P35) was prepared from 1- cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I-12) and (1S)-1-[2-(5- bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethanamine (I-34) by following above protocol in analogy. LCMS (method 2): retention time 1.32 min, m/z 565/567 [M+H]+. 109921 | 83192 FF Example E3: Preparation of N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-1- cyclopropyl-6-(difluoromethyl)-2-oxo-3H-benzimidazole-4-carboxamide (P46) [0369] In a vial containing 1-cyclopropyl-6-(difluoromethyl)-2-oxo-3H-benzimidazole-4-carbonyl fluoride (I- 39) (preparation described below) (70 mg) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]ammonium;chloride (CAS 2739681-96-8, prepared in analogy to descriptions found for example in WO 21/224323) (147 mg) in acetonitrile (3.5 mL) was added N,N-diisopropylethylamine (68 mg) and the mixture was stirred at 22°C for 1 hour. The reaction mixture was then quenched with water and extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) to afford N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-1- cyclopropyl-6-(difluoromethyl)-2-oxo-3H-benzimidazole-4-carboxamide (P46) as a solid. [0370] LCMS (method 1): retention time 0.79 min, m/z 498 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm: 9.67 (s, 1H), 9.22 (d, 1H), 8.75 (d, 1H), 7.89-7.78 (m, 2H), 7.52 (s, 1H), 7.42 (s, 1H), 6.93-6.59 (m, 1H), 6.59-6.47 (m, 1H), 6.01-5.90 (m, 1H), 2.97-2.86 (m, 1H), 2.51 (s, 3H), 1.75 (d, 3H), 1.21-1.14 (m, 2H), 1.08-1.00 (m, 2H). Example E4: Preparation of N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-1-cyclopropyl-N- methyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxamide (P57) [0371] To a mixture of 1-cyclopropyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxylic acid (I-6) (101 mg, 0.353 mmol, 1 equiv.) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-methyl- ammonium chloride (CAS 3024825-36-0, prepared as described in WO 23/247360) (105 mg, 0.424 mmol, 1.2 equiv.) in pyridine (2.8 mL) at 0°C was added phosphorus oxychloride (0.104 mL, 1.06 mmol, 3 equiv.). The reaction mixture was stirred for 1 h at RT, then quenched with aq. NaHCO3 and the product extracted with EtOAc. The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was purified twice by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) to afford N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-1- cyclopropyl-N-methyl-2-oxo-6-(trifluoromethyl)-3H-benzimidazole-4-carboxamide (P57) as a solid. [0372] LCMS (method 1): retention time 0.82 min, m/z 516 [M+H]+. 109921 | 83192 FF Table P: Examples of compounds of formula (I) Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5-cyano-2- pyridyl)-1,2,4-triazol-3- yl]ethyl]-1-cyclopropyl-2- P1 oxo-6-(trifluoromethyl)-3H- 1.05 483 3 benzimidazole-4- carboxamide 1-cyclopropyl-2-oxo-N- [(1S)-1-(2-pyrimidin-2-yl- 1,2,4-triazol-3-yl)ethyl]-6- P2 (trifluoromethyl)-3H- 0.97 459 3 benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- P3 cyclopropyl-2-oxo-6- 1.07 489 3 (trifluoromethyl)-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5- cyclopropyl-1,2,4-triazol-3- P4 yl]ethyl]-1-cyclopropyl-2- 1.69 529 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5-ethyl- 1,2,4-triazol-3-yl]ethyl]-1- P5 cyclopropyl-2-oxo-6- 1.64 517 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- chloropyrimidin-2-yl)-5- methyl-1,2,4-triazol-3- P6 yl]ethyl]-1-cyclopropyl-2- 1.36 507/509 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide 1-cyclopropyl-N-[(1S)-1-[2- (5-fluoropyrimidin-2-yl)-5- methyl-1,2,4-triazol-3- P7 yl]ethyl]-2-oxo-6- 1.27 491 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- carbamoylpyrazin-2-yl)-5- methyl-1,2,4-triazol-3- P8 yl]ethyl]-1-cyclopropyl-2- 1.22 516 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)-5- cyclopropyl-1,2,4-triazol-3- P9 yl]ethyl]-1-cyclopropyl-2- 1.40 542 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- cyclopropyl-1,2,4-triazol-3- P10 yl]ethyl]-1-cyclopropyl-2- 1.53 577/579 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- methyl-1,2,4-triazol-3- P11 yl]ethyl]-1-cyclopropyl-2- 1.38 551/553 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5-methyl- 1,2,4-triazol-3-yl]ethyl]-1- P12 cyclopropyl-2-oxo-6- 1.52 503 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)-5- methyl-1,2,4-triazol-3- P13 yl]ethyl]-1-cyclopropyl-2- 1.25 516 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5-cyano-2- pyridyl)-5-methyl-1,2,4- triazol-3-yl]ethyl]-1- cyclopropyl-2-oxo-6- P14 1.44 497 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- ethyl-1,2,4-triazol-3- P15 yl]ethyl]-1-cyclopropyl-2- 1.48 565/567 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) 1-cyclopropyl-N-[(1S)-1-(5- methyl-2-pyrimidin-2-yl- 1,2,4-triazol-3-yl)ethyl]-2- P16 oxo-6-(trifluoromethyl))-3H- 1.21 473 2 benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- methoxy-1,2,4-triazol-3- P17 yl]ethyl]-1-cyclopropyl-2- 1.43 567/569 2 oxo-6-(trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[5-bromo-2-(5- cyanothiazol-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- P18 cyclopropyl-2-oxo-6- 1.62 567/569 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)- 1,2,4-triazol-3-yl]ethyl]-1- P19 cyclopropyl-2-oxo-6- 1.20 502 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- carbamoylpyrazin-2-yl)- 1,2,4-triazol-3-yl]ethyl]-1- P20 cyclopropyl-2-oxo-6- 1.16 502 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- P21 cyclopropyl-2-oxo-6- 1.33 537/539 2 (trifluoromethyl))-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5-ethyl- 1,2,4-triazol-3-yl]ethyl]-1- P22 cyclopropyl-6- 1.53 515 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5- cyclopropyl-1,2,4-triazol-3- P23 yl]ethyl]-1-cyclopropyl-6- 1.58 527 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- chloropyrimidin-2-yl)-5- methyl-1,2,4-triazol-3- P24 yl]ethyl]-1-cyclopropyl-6- 1.25 505/507 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide 1-cyclopropyl-6- (difluoromethoxy)-N-[(1S)- 1-[2-(5-fluoropyrimidin-2- P25 yl)-5-methyl-1,2,4-triazol-3- 1.16 489 2 yl]ethyl]-2-oxo)-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- carbamoylpyrazin-2-yl)-5- methyl-1,2,4-triazol-3- yl]ethyl]-1-cyclopropyl-6- P26 1.11 514 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- cyclopropyl-1,2,4-triazol-3- P27 yl]ethyl]-1-cyclopropyl-6- 1.42 575/577 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)-5- cyclopropyl-1,2,4-triazol-3- P28 yl]ethyl]-1-cyclopropyl-6- 1.30 540 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- methyl-1,2,4-triazol-3- P29 yl]ethyl]-1-cyclopropyl-6- 1.27 549/551 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5-methyl- 1,2,4-triazol-3-yl]ethyl]-1- P30 cyclopropyl-6- 1.41 501 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)-5- methyl-1,2,4-triazol-3- P31 yl]ethyl]-1-cyclopropyl-6- 1.14 514 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5-cyano-2- pyridyl)-5-methyl-1,2,4- triazol-3-yl]ethyl]-1- P32 cyclopropyl-6- 1.33 495 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- ethyl-1,2,4-triazol-3- P33 yl]ethyl]-1-cyclopropyl-6- 1.37 563/565 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide 1-cyclopropyl-6- (difluoromethoxy)-N-[(1S)- 1-(5-methyl-2-pyrimidin-2- P34 yl-1,2,4-triazol-3-yl)ethyl]-2- 1.10 471 2 oxo)-3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- methoxy-1,2,4-triazol-3- P35 yl]ethyl]-1-cyclopropyl-6- 1.32 565/567 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[5-bromo-2-(5- cyanothiazol-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- P36 cyclopropyl-6- 1.51 565/567 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5-cyano-2- pyridyl)-1,2,4-triazol-3- yl]ethyl]-1-cyclopropyl-6- (difluoromethoxy)-2-oxo)- P37 1.26 481 2 3H-benzimidazole-4- carboxamide 1-cyclopropyl-6- (difluoromethoxy)-2-oxo-N- [(1S)-1-(2-pyrimidin-2-yl- P38 1,2,4-triazol-3-yl)ethyl])-3H- 1.06 457 2 benzimidazole-4- carboxamide N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)- 1,2,4-triazol-3-yl]ethyl]-1- P39 cyclopropyl-6- 1.08 500 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- P40 cyclopropyl-6- 1.34 487 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- P41 cyclopropyl-6- 1.22 535/537 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- carbamoylpyrazin-2-yl)- 1,2,4-triazol-3-yl]ethyl]-1- P42 cyclopropyl-6- 1.05 500 2 (difluoromethoxy)-2-oxo)- 3H-benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5- cyclopropyl-1,2,4-triazol-3- P43 yl]ethyl]-1-cyclopropyl-6- 1.01 511 1 (difluoromethyl)-2-oxo-3H- benzimidazole-4- carboxamide 1-cyclopropyl-6- (difluoromethyl)-N-[(1S)-1- [2-(5-fluoropyrimidin-2-yl)- P44 5-methyl-1,2,4-triazol-3- 0.80 473 1 yl]ethyl]-2-oxo-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- cyanothiazol-2-yl)-5-methyl- 1,2,4-triazol-3-yl]ethyl]-1- P45 cyclopropyl-6- 0.93 485 1 (difluoromethyl)-2-oxo-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)-5- methyl-1,2,4-triazol-3- P46 yl]ethyl]-1-cyclopropyl-6- 0.79 498 1 (difluoromethyl)-2-oxo-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- carbamoylpyrazin-2-yl)- 1,2,4-triazol-3-yl]ethyl]-1- cyclopropyl-6- P47 0.75 484 1 (difluoromethyl)-2-oxo-3H- benzimidazole-4- carboxamide 1-cyclopropyl-2-oxo-N- [(1S)-1-(2-pyrazin-2-yl- 1,2,4-triazol-3-yl)ethyl]-6- P48 (trifluoromethyl)-3H- 1.31 459 2 benzimidazole-4- carboxamide N-[(1S)-1-[3-(5-cyano-2- pyridyl)pyrazin-2-yl]ethyl]-1- cyclopropyl-2-oxo-6- (trifluoromethyl)-3H- P49 benzimidazole-4- 1.49 494 2 carboxamide 1-cyclopropyl-N-[(1S)-1-[2- (1-methyl-6-oxo-pyridazin- 3-yl)-1,2,4-triazol-3- P50 yl]ethyl]-2-oxo-6- 1.21 489 2 (trifluoromethyl)-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(6- cyanopyrimidin-4-yl)-1,2,4- triazol-3-yl]ethyl]-1- P51 cyclopropyl-2-oxo-6- 1.44 484 2 (trifluoromethyl)-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- bromopyrazin-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- cyclopropyl-2-oxo-6- P52 (trifluoromethyl)-3H- 1.54 537/539 2 benzimidazole-4- carboxamide 1-cyclopropyl-N-[(1S)-1-[2- (6-methoxypyridazin-3-yl)- 1,2,4-triazol-3-yl]ethyl]-2- oxo-6-(trifluoromethyl)-3H- P53 1.37 489 2 benzimidazole-4- carboxamide 1-cyclopropyl-6- (difluoromethoxy)-N-[(1S)- 1-[2-[6- (difluoromethyl)pyrimidin-4- P54 1.43 521 2 yl]-5-methyl-1,2,4-triazol-3- yl]ethyl]-2-oxo-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(5- chloropyrazin-2-yl)-1,2,4- triazol-3-yl]ethyl]-1- cyclopropyl-2-oxo-6- P55 1.45 493/495 2 (trifluoromethyl)-3H- benzimidazole-4- carboxamide 109921 | 83192 FF Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- chloropyrazin-2-yl)-5- methyl-1,2,4-triazol-3- P56 yl]ethyl]-1-cyclopropyl-2- 1.52 507/509 2 oxo-6-(trifluoromethyl)-3H- benzimidazole-4- carboxamide N-[(1S)-1-[2-(6- carbamoylpyrimidin-4-yl)- 1,2,4-triazol-3-yl]ethyl]-1- P57 cyclopropyl-N-methyl-2- 0.82 516 1 oxo-6-(trifluoromethyl)-3H- benzimidazole-4- carboxamide Preparation of intermediates Example PI-1: Preparation of 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I- 12) (I-12) Step 1: Preparation of methyl 3-(cyclopropylamino)-5-fluoro-2-nitro-benzoate (I-7) [0373] To a stirred solution of methyl 3,5-difluoro-2-nitro-benzoate (CAS 910123-09-0) (10.0 g, 46.1 mmol) in acetonitrile (300 mL) were added potassium carbonate (12.9 g, 92.2 mmol) and cyclopropylamine (3.51 mL, 50.7 mmol). The suspension was heated to 60°C for 2 hours, then cooled to room temperature and diluted with water. The product was extracted with ethyl acetate, the combined organic phases washed with brine, dried 109921 | 83192 FF over anhydrous sodium sulfate, filtered and concentrated in vacuo to afford crude methyl 3-(cyclopropylamino)- 5-fluoro-2-nitro-benzoate (I-7) as a solid. This material was used as such in the following step. [0374] 1H NMR (400 MHz, CDCl3) δ ppm 7.78 (br s, 1H), 7.03 (dd, 1H), 6.54 (dd, 1H), 3.90 (s, 3H), 2.60- 2.54 (m, 1H), 0.99-0.92 (m, 2H), 0.70-0.63 (m, 2H). Step 2: Preparation of methyl 3-(cyclopropylamino)-5-hydroxy-2-nitro-benzoate (I-8) [0375] To a solution of methyl 3-(cyclopropylamino)-5-fluoro-2-nitro-benzoate (I-7) (preparation described hereabove) (8.0 g, 31.0 mmol) in anhydrous N,N-dimethylformamide (160 mL) under inert atmosphere was added 2-(methylsulfonyl)ethanol (5.8 g, 47 mmol). The solution was cooled to 0°C and sodium hydride (60% suspension in paraffin oil, 3.7 g, 93 mmol) was added portionwise over 20 minutes. The reaction mixture was stirred for 1.5 hours, then very carefully quenched with 1M aqueous HCl. The mixture was extracted with ethyl acetate, the combined organic layers washed with 1M aqueous HCl, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified twice by chromatography over silica gel (gradient ethyl acetate in cyclohexane) to afford methyl 3-(cyclopropylamino)-5-hydroxy-2-nitro-benzoate (I-8) as a solid. [0376] LCMS (method 1): retention time 0.83 min, m/z 253 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 8.05 (br s, 1H), 6.72 (d, 1H), 6.55 (br s, 1H), 6.30 (d, 1H), 3.91 (s, 3H), 2.52-2.58 (m, 1H), 0.96-0.90 (m, 2H), 0.69- 0.63 (m, 2H). Step 3: Preparation of methyl 3-(cyclopropylamino)-5-(difluoromethoxy)-2-nitro-benzoate (I-9) [0377] To a solution of methyl 3-(cyclopropylamino)-5-hydroxy-2-nitro-benzoate (I-8) (preparation described hereabove) (5.6 g, 22.2 mmol) in N,N-dimethylformamide (40 mL) were added sodium chlorodifluoroacetate (3.72 g, 24.4 mmol), sodium carbonate (2.87 g, 26.6 mmol) and water (0.57 mL). The reaction mixture was stirred at 80°C for 3 hours, then cooled to room temperature. Water (100 mL) was added, and the mixture extracted with ethyl acetate (200 mL). The organic phase was washed with water (200 mL), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography over silica gel (gradient ethyl acetate in cyclohexane) to afford methyl 3-(cyclopropylamino)-5- (difluoromethoxy)-2-nitro-benzoate (I-9). 109921 | 83192 FF [0378] LCMS (method 1): retention time 1.03 min, m/z 303 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 7.76 (br s, 1H), 7.06 (d, 1H), 6.62 (t, J=72.5Hz, 1H), 6.54 (d, 1H), 3.90 (s, 3H), 2.60-2.56 (m, 1H), 0.98-0.93 (m, 2H), 0.69-0.64 (m, 2H). Step 4: Preparation of methyl 2-amino-3-(cyclopropylamino)-5-(difluoromethoxy)benzoate (I-10) [0379] A solution of methyl 3-(cyclopropylamino)-5-(difluoromethoxy)-2-nitro-benzoate (I-9) (preparation described hereabove) (2.0 g, 6.62 mmol) in methanol (130 mL) was flushed with argon for 5 minutes. Palladium on charcoal (10%) (300 mg) was added, the suspension sparged with hydrogen and the mixture stirred at 23°C for 100 minutes under a slight overpressure of hydrogen (balloon). The reaction mixture was flushed with argon for 15 minutes and filtered through a bed of Celite. The residue was rinsed with methanol and the filtrate evaporated under reduced pressure to afford crude methyl 2-amino-3-(cyclopropylamino)-5- (difluoromethoxy)benzoate (I-10) as an oil. This material was used as such in the following step. [0380] LCMS (method 1): retention time 1.00 min, m/z 273 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 7.19 (br d, 1H), 6.99 (d, 1H), 6.45 (t, J=74.8Hz, 1H), 5.84-4.29 (br m, 3H), 3.89 (s, 3H), 2.51-2.43 (m, 1H), 0.83-0.76 (m, 2H), 0.60-0.53 (m, 2H). Step 5: Preparation of methyl 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylate (I-11) [0381] To a solution of methyl 2-amino-3-(cyclopropylamino)-5-(difluoromethoxy)benzoate (I-10) (preparation described hereabove) (1.8 g, 6.61 mmol) in anhydrous tetrahydrofuran (35 mL) at 0°C under inert atmosphere was added triphosgene (bis(trichloromethyl)carbonate; 1.962 g, 6.61 mmol), followed by N,N- diisopropylethylamine (3.43 mL, 19.84 mmol) dropwise over five minutes. The reaction mixture was stirred for 80 minutes, then carefully poured onto water (150 mL) and extracted with ethyl acetate (300 mL). The combined organic layers were washed with a saturated aqueous ammonium chloride solution, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was triturated with diisopropyl ether/EtOAc 14:1 (7.5 mL), the mixture filtered and the solid dried in vacuo to afford methyl 1-cyclopropyl-6-(difluoromethoxy)-2- oxo-3H-benzimidazole-4-carboxylate (I-11). 109921 | 83192 FF [0382] LCMS (method 1): retention time 0.85 min, m/z 299 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 8.99 (br s, 1H), 7.42 (d, 1H), 7.17 (d, 1H), 6.52 (t, J=73.6Hz, 1H), 3.98 (s, 3H), 2.89 (m, 1H), 1.19-1.12 (m, 2H), 1.07-1.00 (m, 2H). Step 6: Preparation of 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I-12) (I-12) [0383] To a suspension of methyl 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylate (I-11) (preparation described hereabove) (1.9 g, 6.37 mmol) in tetrahydrofuran (25 mL) were added water (12 mL) and lithium hydroxide monohydrate (324 mg, 7.64 mmol). The mixture was stirred at 50°C for 19 hours, then poured onto water (100 mL) and extracted with tert-butyl methyl ether (300 mL). The aqueous phase was acidified by dropwise addition of aqueous 1 M HCl and the resulting suspension thoroughly extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was triturated with diisopropyl ether/DCM 3:1 (8 mL), the mixture filtered and the solid dried in vacuo to afford 1-cyclopropyl-6-(difluoromethoxy)-2-oxo-3H-benzimidazole-4-carboxylic acid (I-12). [0384] LCMS (method 1): retention time 0.74 min, m/z 285 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 13.39 (br s, 1H), 10.69 (s, 1H), 7.23 (d, 1H), 7.20 (t, J=74.3Hz, 1H), 7.19 (d, 1H), 2.86 (m, 1H), 1.04-0.98 (m, 2H), 0.96-0.91 (m, 2H). 19F NMR (377 MHz, CDCl3) δ ppm -81.46 (s). Example PI-2: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 23) Step 1: Preparation of (5-bromopyrimidin-2-yl)hydrazine (I-16) [0385] To a solution of 5-bromo-2-chloro-pyrimidine (15.0 g, 77.55 mmol) in methanol (150 mL) was added hydrazine hydrate (10.1 mL, 155.1 mmol, 2.0 equiv.) at 0°C. After addition, the reaction mixture was stirred at room temperature, then at 60°C for 6 hours. Upon cooling to room temperature, the formed solid was filtered 109921 | 83192 FF and dried in vacuo to afford (5-bromopyrimidin-2-yl)hydrazine (I-16) as an off-white solid (11.0 g). This material was used without further purification in the next step. [0386] 1H NMR (400 MHz, DMSO-d6) δ ppm 8.48 (s, 1H), 8.40 (s, 2H), 4.20 (s, 2H). Step 2: Preparation of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17) [0387] tert-Butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (CAS 85642-13-3) (70.0 g, 353 mmol, 1 equiv.) was mixed with 2-methyltetrahydrofuran (1.12 L) and N,N-dimethylformamide-dimethylacetal (DMF- DMA, 70 mL, 530 mmol, 1.5 equiv.), and the mixture heated to 40°C for 2 hours. The reaction mixture was concentrated under reduced pressure to yield the title compound (I-17) (105g, 97% yield, 80% purity). [0388] 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.39 (s, 1H), 6.69 (br d, 1H), 3.97 (quint, 1H), 3.13 (s, 3H), 3.00 (s, 3H), 1.38 (s, 9H), 1.22 (d, 3H). [0389] Similarly, tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) was prepared from tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (CAS 85642-13-3) and N,N-dimethylacetamide-dimethyl acetal (CAS 18871-66-4) by following above protocol in analogy. [0390] 1H NMR (400 MHz, CDCl3) δ ppm: 5.50-5.40 (m, 1H), 4.30-4.20 (m, 1H), 3.08 (s, 6H), 2.24 (s, 3H), 1.45 (s, 9H), 1.38 (d, 3H). Step 3: Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-19) [0391] To a mixture of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17, prepared as described above) (7.73 g, 30.5 mmol, 1.2 equiv.) in 1,4-dioxane (32 mL) were added (5-bromopyrimidin-2-yl)hydrazine (I-16) (5.0 g, 25.4 mmol, 1.0 equiv.) and acetic acid (32 mL). The reaction mixture was stirred at 75°C for 3 hours, then concentrated under reduced pressure. The solid residue was diluted with EtOAc and water, the layers separated, the aqueous phase extracted with EtOAc, the combined organic layers washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. 109921 | 83192 FF The residue was purified with flash column chromatography over silica gel (tert-butyl methyl ether in dichloromethane) to provide the desired product (I-19) as a solid. [0392] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.21 (s, 2H), 8.18 (s, 1H), 7.53 (br d, 1H), 5.50 (quint, 1H), 1.45 (d, 3H), 1.31 (s, 9H). [0393] Similarly, tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-20) was prepared from tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) and (5-bromopyrimidin-2-yl)hydrazine (I-16) by applying above protocol in analogy. [0394] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.14 (s, 2H), 7.45 (br d, 1H), 5.47 (quint, 1H), 2.33 (s, 3H), 1.42 (d, 3H), 1.29 (s, 9H). [0395] Similarly, tert-butyl N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-21) was prepared from tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) and (5-fluoropyrimidin-2-yl)hydrazine (CAS 104408-28-8) by applying above protocol in analogy. [0396] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.06 (s, 2H), 7.41 (br d, 1H), 5.40 (quint, 1H), 2.31 (s, 3H), 1.43 (d, 3 H), 1.28 (s, 9H). (I-21) [0397] Similarly, tert-butyl N-[(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-22) was prepared from tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) and (5-chloropyrimidin-2-yl)hydrazine (CAS 823-90-5) by applying above protocol in analogy. [0398] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.09 (s, 2H), 7.44 (d, 1H), 5.45 (quint, 1H), 2.33 (s, 3H), 1.42 (d, 3H), 1.30 (s, 9H). 109921 | 83192 FF Step 4: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23) [0399] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I- 19) (5.4 g, 14.6 mmol) in 1,4-dioxane (73 mL) was added a 4.0 M solution of hydrochloric acid in 1,4-dioxane (39 mL, 156 mmol) dropwise at 0°C. The reaction mixture was stirred at room temperature for 5 hours, then concentrated under reduced pressure. The residue was triturated with EtOAc, filtered and the solid dried in vacuo to provide [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23). [0400] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.22 (s, 2H), 8.84 (br s, 3H), 8.39 (s, 1H), 5.29 (br m, 1H), 1.64 (d, 3H). LCMS (method 3): retention time 0.17 min, m/z 269/271 [M+H]+ for the corresponding free base. [0401] Similarly, [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 24) was prepared from tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-20) by applying above protocol in analogy. [0402] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.18 (s, 2H), 8.74 (br s, 3H), 5.25 (m, 1H), 2.41 (s, 3H), 1.61 (d, 3H). [0403] Similarly, [(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 25) was prepared from tert-butyl N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-21) by applying above protocol in analogy. [0404] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.11 (s, 2H), 8.72 (br s, 3H), 5.22 (m, 1H), 2.41 (s, 3H), 1.61 (d, 3H). 109921 | 83192 FF [0405] Similarly, [(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 26) was prepared from tert-butyl N-[(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-22) by applying above protocol in analogy. [0406] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.12 (s, 2H), 8.78 (br s, 3H), 5.25 (m, 1H), 2.40 (s, 3H), 1.61 (d, 3H). Example PI-3: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-31) Step 1: Preparation of tert-butyl N-[(1S)-2-[[amino(cyclopropyl)methylene]amino]-1-methyl-2-oxo- ethyl]carbamate (I-27) [0407] To a solution of (2S)-2-(tert-butoxycarbonylamino)propanoic acid (5.00 g, 26.4 mmol, 1.0 equiv.) and cyclopropanecarboximidoylammonium chloride (5.74 g, 47.6 mmol, 1.8 equiv.) in N,N-dimethylformamide (130 mL) at room temperature was added 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3- oxide hexafluorophosphate (HATU, CAS 148893-10-1) (20.1 g, 2.0 equiv.), followed by N,N- 109921 | 83192 FF diisopropylethylamine (12.2 g, 3.5 equiv.). The reaction mixture was stirred at room temperature for 5 hours to afford tert-butyl N-[(1S)-2-[[amino(cyclopropyl)methylene]amino]-1-methyl-2-oxo-ethyl]carbamate (I-27), which was not isolated. TLC (70% EtOAc in cyclohexane): Rf = 0.21. [0408] Similarly, tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-ethyl]carbamate (I-28) was prepared from (2S)-2-(tert-butoxycarbonylamino)propanoic acid and propanimidoyl-ammonium chloride by applying above protocol in analogy. TLC (50% EtOAc in cyclohexane): Rf = 0.12. Step 2: Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-29) [0409] To above solution in N,N-dimethylformamide of tert-butyl N-[(1S)-2- [[amino(cyclopropyl)methylene]amino]-1-methyl-2-oxo-ethyl]carbamate (I-27) were added (5-bromopyrimidin- 2-yl)hydrazine (I-16, prepared as described above) (7.99 g, 1.6 equiv.) and acetic acid (16.70 g, 10.0 equiv.). The reaction mixture was heated at 45°C for 90 minutes, then at 60°C for 1 hour. After cooling to room temperature, the mixture was diluted with a saturated aqueous solution of sodium carbonate, and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient ethyl acetate in cyclohexane) to afford tert-butyl N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-29) as a colorless solid. [0410] 1H NMR (400 MHz, CDCl3) δ ppm: 8.85 (s, 2H), 5.85 (quint, 1H), 5.59 (d, 1H), 2.15 (m, 1H), 1.49 (d, 3H), 1.43 (s, 9 H), 1.10-0.97 (m, 4H). [0411] Similarly, tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I- 30) was prepared from tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-ethyl]carbamate (I-28) and (5-bromopyrimidin-2-yl)hydrazine (I-16) by applying above protocol in analogy. [0412] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.15 (s, 2H), 7.46 (d, 1H), 5.46 (quint, 1H), 2.69 (q, 2H), 1.41 (d, 3H), 1.30 (s, 9 H), 1.25 (t, 3H). 109921 | 83192 FF Step 3: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-31) [0413] tert-Butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-29) (3.2 g, 7.8 mmol) was added to a 4.0 M solution of HCl in ethyl acetate (64.0 mL, 33 equiv.) stirred at 0°C. The reaction mixture was stirred at room temperature for two hours, then evaporated under reduced pressure. The obtained solid material was washed with ethyl acetate and dried in vacuo to afford [(1S)-1-[2-(5- bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-31) as a light yellow solid. [0414] LCMS (method 3): retention time 0.55 min, m/z 309/311 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.15 (s, 2H), 8.76 (br s, 3H), 5.21 (m, 1H), 2.15-2.05 (m, 1H), 1.59 (d, 3H), 1.08-1.02 (m, 2H), 0.95-0.83 (m, 2H). [0415] Similarly, [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-32) was prepared from tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I- 30) by applying above protocol in analogy. [0416] LCMS (method 3): retention time 0.57 min, m/z 297/299 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.18 (s, 2H), 8.71 (br s, 3H), 5.26 (m, 1H), 2.77 (q, 2H), 1.61 (d, 3H), 1.30 (t, 3H). (I-32) Example PI-4: Preparation of (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethanamine (I-34) 109921 | 83192 FF Step 1: Preparation of 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethyl]isoindoline-1,3- dione (I-33) [0417] To a solution of O-methyl N-[(2S)-2-(1,3-dioxoisoindolin-2-yl)propanoyl]carbamothioate (CAS 2592405-42-8, prepared as described in WO21/165195) (8.4 g, 90 mass%, 26 mmol) in ethanol (170 mL) was added (5-bromopyrimidin-2-yl)hydrazine (I-16) (5.7 g, 1.1 equiv.) at room temperature. The reaction mixture was stirred at 90°C for 5 hours, then cooled to room temperature and diluted with water. The product was extracted with ethyl acetate, the combined organic layers washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by chromatography on silica gel (gradient ethyl acetate in cyclohexane) to afford 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4- triazol-3-yl]ethyl]isoindoline-1,3-dione (I-33) as a colorless solid. [0418] LCMS (method 3): retention time 1.10 min, m/z 429/431 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.94 (s, 2H), 7.84 (s, 4H), 6.05 (q, 1H), 3.95 (s, 3H), 1.78 (d, 3H). Step 2 Preparation of (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethanamine (I-34) (I-34) [0419] To a solution of 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethyl]isoindoline- 1,3-dione (I-33) (3.0 g, 6.29 mmol) in ethanol (60 mL) was added hydrazine hydrate (0.794 g, 15.7 mmol, 2.5 equiv.) dropwise. The reaction mixture was stirred for 16 hours at room temperature, then the suspension was filtered, and the residue washed with ethanol. The combined filtrates were concentrated under reduced 109921 | 83192 FF pressure and the obtained solid dried in vacuo to afford (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4- triazol-3-yl]ethanamine (I-34) as an off-white solid. [0420] LCMS (method 3): retention time 0.44 min, m/z 299/301 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.10 (s, 2H), 4.64 (q, 1H), 3.93 (s, 3H), 3.04-3.26 (br s, 2H), 1.37 (d, 3H). Example PI-5: Preparation of [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38) (I-38) Step 1: Preparation of ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1-yl]thiazole-5- carboxylate (I-35) [0421] Ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1-yl]thiazole-5-carboxylate (I-35) was prepared from tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-ethyl]carbamate (I- 28) and ethyl 2-hydrazinothiazole-5-carboxylate (CAS 859485-62-4) by applying above protocol ‘Example PI- 3, step 2’ in analogy. [0422] LCMS (method 3): retention time 1.25 min, m/z 396 [M+H]+. Step 2: Preparation of tert-butyl N-[1-[2-(5-carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I- 36) (I-36) [0423] A mixture of ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1-yl]thiazole-5- carboxylate (I-35) (5.4 g, 14.2 mmol) and a 2.0 M solution of ammonia in EtOH (540 mL) was stirred at 20°C 109921 | 83192 FF for 18 hours. The reaction mixture was evaporated under reduced pressure, the solid residue triturated twice with tert-butyl methyl ether (300 mL, then 100 mL), filtered and dried in vacuo to afford tert-butyl N-[1-[2-(5- carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-36) as a solid. [0424] 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.25 (s, 2H), 7.77 (s, 1H), 7.61 (d, 1H), 5.55 (quint, 1H), 2.68 (q, 2H), 1.40 (d, 3H), 1.34 (s, 9 H), 1.23 (t, 3H). Step 3: Preparation of tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I- 37) (I-37) [0425] To a solution of tert-butyl N-[1-[2-(5-carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-36) (4.0 g, 10.9 mmol) in acetonitrile (40 mL) at 20°C was added triethylamine (4.7 mL, 33.6 mmol). The mixture was cooled to 0°C and trifluoroacetic anhydride (3.1 mL, 22.0 mmol) was added dropwise within 10 minutes. After addition, stirring was continued for 30 minutes, then water (100 mL) was carefully added, and the product extracted with EtOAc (total 160 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography over silica gel (gradient EtOAc in cyclohexane) to afford tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-37). [0426] 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.62 (s, 1H), 7.64 (d, 1H), 5.52 (quint, 1H), 2.69 (q, 2H), 1.39 (d, 3H), 1.33 (s, 9 H), 1.22 (t, 3H). Step 4: Preparation of [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 38) [0427] [(1S)-1-[2-(5-Cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38) was prepared from tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-37) by applying above protocol ‘Example PI-3, step 3’ in analogy. [0428] LCMS (method 3): retention time 0.98 min, m/z 249 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.78 (br s, 3H), 8.69 (s, 1H), 5.30 (m, 1H), 2.79 (q, 2H), 1.62 (d, 3H), 1.30 (t, 3H). 109921 | 83192 FF Example PI-6: Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium;2,2,2- trifluoroacetate (I-14) Step 1: Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-13) [0429] To a solution of tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (1.8 g, 9.56 mmol) in 2- methyltetrahydrofuran (29 mL) was added N,N-dimethylformamide dimethyl acetal (14.35 mmol) at room temperature. The resulting reaction mixture was stirred at 40°C for 1.5 hour, then concentrated in vacuo to get the crude intermediate tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17). [0430] 1,4-Dioxane (9.6 mL), acetic acid (9.6 mL) and 2-bromo-5-hydrazinylpyrazine (CAS 1001050-24-3) (1.6 g, 95%, 8.04 mmol) were added to this intermediate and the mixture was stirred at 80°C for 2 hours, then cooled to room temperature and poured over water and EtOAc. The phases were separated, the aqueous layer extracted with EtOAc, the combined organic layers washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by combiflash (ethyl acetate in cyclohexane) to afford tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-13) as a gum. LCMS (method 1): retention time 0.95 min, m/z 369/371 [M+H]+. [0431] Similarly, tert-butyl N-[(1S)-1-[2-(5-chloropyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-41) was prepared from tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate and 2-chloro-5-hydrazinylpyrazine (prepared as described in WO 2021/126923) by applying above protocol in analogy. LCMS (method 3): retention time 1.09 min, m/z 325/327 [M+H]+. Step 2: Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium;2,2,2- trifluoroacetate (I-14) 109921 | 83192 FF [0432] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-13) (2.0 g, 5.52 mmol) in trifluoromethylbenzene (40 mL) was added 2,2,2-trifluoroacetic acid (10mL) dropwise at RT and the reaction mixture was stirred for 2.5 h. The mixture was evaporated to dryness under reduced pressure, the oily residue triturated with TBME, and the resulting solid filtered and dried in vacuo to afford [(1S)- 1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium;2,2,2-trifluoroacetate (I-14) as an off-white solid. [0433] LCMS (method 3): retention time 0.3 min, m/z 269/271 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm 9.08 (s, 1H) 8.93 (s, 1H), 8.61 (br s, 3H), 8.50 (s, 1H), 5.27 (q, 1H), 1.60 (d, 3H). Example PI-7: Preparation of 1-cyclopropyl-6-(difluoromethyl)-2-oxo-3H-benzimidazole-4-carbonyl fluoride (I- 39) Step 1: Preparation of methyl 3-(cyclopropylamino)-2-nitro-benzoate [0434] To a solution of methyl 3-fluoro-2-nitro-benzoate (CAS 1214353-57-7) (5.00 g) in acetonitrile (125 mL) were added cyclopropyl amine (1.93 mL) and potassium carbonate (6.95 g). The suspension was stirred at 60°C for 20 hours. After conversion, the reaction mixture was cooled, then quenched with water and extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) to afford the title compound. [0435] 1H NMR (400 MHz, CDCl3) δ ppm 7.50-7.39 (m, 3H), 6.86 (d, 1H), 3.90 (s, 3H), 2.64-2.46 (m, 1H), 0.96-0.91 (m, 2H), 0.68-0.60 (m, 2H). Step 2: Preparation of methyl 2-amino-3-(cyclopropylamino)benzoate [0436] To a solution of methyl 3-(cyclopropylamino)-2-nitro-benzoate (preparation described hereabove) (28.4 g) in methanol (360 mL) were added zinc powder (54.9 g), followed by acetic acid (34.7 mL). The mixture was stirred at 35-60°C for 1 hour and 20 minutes. The mixture was then cooled, diluted with ethyl acetate (200 109921 | 83192 FF mL) and filtered. The filtrate was made alkaline by adding an aqueous solution of sodium hydroxide and the product extracted with ethyl acetate (600 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) to afford the title compound [0437] 1H NMR (400 MHz, CDCl3) δ ppm 7.50 (d, 1H), 7.21 (d, 1H), 6.78 (t, 1H), 3.91 (s, 3H), 2.54-2.47 (m, 1H), 0.81-0.76 (m, 2H), 0.59-0.54 (m, 2H). Step 3: Preparation of methyl 1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylate [0438] To a solution of methyl 2-amino-3-(cyclopropylamino)benzoate (preparation described hereabove) (6.3 g) in tetrahydrofuran (150 mL) at 0°C was added triphosgene (9.05 g). After 10 minutes, N,N- diisopropylethylamine (15.8 mL) was added and the reaction mixture was stirred at room temperature for 18 hours. After quenching with water (150 mL), the mixture was extracted with ethyl acetate. The combined organic layers were washed with a saturated aqueous solution of ammonium chloride, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo. The crude compound was submitted to flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) to afford the title compound. [0439] 1H NMR (400 MHz, CDCl3) δ ppm 8.97 (br s, 1H), 7.65 (d, 1H), 7.35 (d, 1H), 7.12 (t, 1H), 3.97 (s, 3H), 2.90 (tt, 1H), 1.18-1.10 (m, 2H), 1.07-1.00 (m, 2H). Step 4: Preparation of methyl 6-bromo-1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylate [0440] To a solution of methyl 1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylate (preparation described hereabove) (4.5 g) in acetic acid (97 mL) at 23°C was added bromine (3.4 g). After stirring for 3.6 hours, another portion of bromine (3.4 g) was added, and stirring was continued for another 3.25 hours. The reaction mixture was quenched with water (200 mL), then with an aqueous solution of sodium thiosulfate until all bromine was consumed. The resulting mixture was extracted with ethyl acetate (750 mL), the organic phase was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was submitted to flash chromatography over silica gel (gradient ethyl acetate in cyclohexane). After evaporation of the selected fractions, the residue was triturated with chloroform (150 mL), then with diethyl ether. The title compound was isolated by filtration as colorless crystals. 109921 | 83192 FF [0441] 1H NMR (400 MHz, CDCl3) δ ppm 9.05 (br s, 1H), 7.80 (s, 1H), 7.47 (s, 1H), 3.97 (s, 3H), 2.92-2.86 (m, 1H), 1.19-1.15 (m, 2H), 1.08-1.01 (m, 2H). Step 5: Preparation of 6-bromo-1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylic acid [0442] To a solution of methyl 6-bromo-1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylate (preparation described hereabove) (5.9 g) in methanol (190 mL) at ambient temperature were added water (67 mL) and lithium hydroxide monohydrate (2.42 g). The mixture was heated to 45°C and stirred for 15 hours. The volatiles were removed under reduced pressure and the residue was treated with 1M aqueous sodium hydroxide (150 mL), then washed with TBME (500 mL). The aqueous phase was then acidified with aqueous 4M HCl and the precipitate was collected by filtration, washed with water and dried in vacuo to yield the title compound as a colorless solid. [0443] 1H NMR (400 MHz, DMSO-d6) δ ppm 13.43 (br s, 1H), 10.78 (s, 1H), 7.58 (s, 1H), 7.47 (s, 1H), 2.91- 2.84 (m, 1H), 1.08-1.01 (m, 2H), 0.92-0.84 (m, 2H). Step 6: Preparation of 1-cyclopropyl-2-oxo-6-vinyl-3H-benzimidazole-4-carboxylic acid [0444] To a solution of 6-bromo-1-cyclopropyl-2-oxo-3H-benzimidazole-4-carboxylic acid (preparation described hereabove) (2.5 g) in ethanol (60 mL) and water (25 mL) under argon was added potassium vinyltrifluoroborate (1.69 g). The mixture was flushed with argon 10 minutes, then potassium carbonate (3.52 g) was added, followed by dichloro[1,1’-bis(diphenylphosphino)ferrocene]palladium (II) (0.778 g). The mixture was heated to 85°C for 17 hours. The volatiles were removed under reduced pressure, 1M aqueous sodium hydroxide (120 mL) was added and the resulting mixture was washed with TBME (500 mL). The aqueous phase was then freed from volatiles under reduced pressure and acidified with 4M aqueous HCl (100 mL). The mixture was extracted with ethyl acetate (600 mL), the combined organic layers dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to afford the title compound. This material was used in the following step without purification. [0445] LCMS (method 1): retention time 0.76 min, m/z 243 [M-H]-. Step 7: Preparation of 1-cyclopropyl-6-formyl-2-oxo-3H-benzimidazole-4-carboxylic acid 109921 | 83192 FF [0446] A solution of crude 1-cyclopropyl-2-oxo-6-vinyl-3H-benzimidazole-4-carboxylic acid (preparation described hereabove) (1.1 g) in acetone (200 mL) and water (20 mL) was stirred in an ice bath. A flow of ozone (1.85 equivalent) in oxygen was bubbled through it, then the mixture was bubbled through with argon for more than 10 minutes. An aliquot of the reaction mixture was submitted to LCMS analysis and showed that all the starting material was consumed. The reaction mixture was then treated with an aqueous solution of sodium metabisulfite until no peroxide was detected. The acetone was evaporated under reduced pressure and the residue treated with 1M aqueous sodium hydroxide. The resulting mixture was washed with diethyl ether and excess ether was blown away by bubbling argon through the mixture. The mixture was then acidified with aqueous HCl and the suspension isolated by filtration. The solid residue was washed with water and dried in vacuo to afford the crude title compound. This material was used in the following step without purification. [0447] LCMS (method 1): retention time 0.72 min, m/z 245 [M-H]-. Step 8: Preparation of 1-cyclopropyl-6-(difluoromethyl)-2-oxo-3H-benzimidazole-4-carbonyl fluoride (I-39) (I-39) [0448] A suspension of crude 1-cyclopropyl-6-formyl-2-oxo-3H-benzimidazole-4-carboxylic acid (preparation described hereabove) (0.45 g) in dichloromethane (9 mL) was stirred in an ice bath. N-ethyl-N- (trifluoro-λ⁴-sulfanyl)ethanamine (DAST) (2.54 ml, 10 equiv.) was added neat over 1.5 minute. The reactor was tightly closed and the mixture stirred overnight at RT. The reaction mixture was poured slowly into well stirred ice water (strong reaction of the excess DAST), then the mixture was extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered and carefully evaporated in vacuo without heating to afford the title compound. This material was used directly in the following step without purification [0449] LCMS (method 1): retention time 0.98 min, m/z 251 [M-F]+ (acylium cation). 19F NMR (377 MHz, CDCl3) δ ppm 24 (s), -108 (s). Example PI-8: Preparation of [(1S)-1-[2-(5-carbamoylpyrazin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-40) 109921 | 83192 FF [0450] Compound (I-40) was prepared by following in analogy the synthesis route for [(1S)-1-[2-(5- carbamoylpyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 3024825-20-2) outlined in WO 23/247360 (Example PI-4 on page 147), but replacing N,N-dimethylformamide dimethyl acetal with N,N- dimethylacetamide-dimethyl acetal (CAS 18871-66-4) in step 1. [0451] LCMS (method 3): retention time 0.22 min, m/z 248 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.62 (d, 3H), 2.45 (s, 3H), 5.30 (m, 1H), 7.96 (s, 1H), 8.35 (s, 1H), 8.86 (br s, 3H), 9.11 (s, 1H), 9.14 (s, 1H). Example PI-9: Preparation of [(1S)-1-[2-(5-chloropyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 42) (I-42) [0452] To a solution of tert-butyl N-[(1S)-1-[2-(5-chloropyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-41) (preparation described hereabove) (1 g) in 1,4-dioxane (8 mL) was added a 4.0 M solution of HCl in 1,4- dioxane (8.2 mL) at RT. The reaction mixture was stirred for 3.5 hours, then concentrated in vacuo to afford [(1S)-1-[2-(5-chloropyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-42) as a solid. [0453] LCMS (method 3): retention time 0.43 min, m/z 225/227 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm 9.08 (s, 1H), 8.88 (br s, 4H), 8.47 (s, 1H), 5.24 (q, 1H), 1.63 (d, 3H). Table PI: Intermediate compounds Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured) 7-bromo-3-cyclopropyl-5- (trifluoromethyl)-1H- benzimidazol-2-one I-4 1.09 321/323 3 109921 | 83192 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured) methyl 1-cyclopropyl-2-oxo- 6-(trifluoromethyl)-3H- benzimidazole-4- I-5 carboxylate 1.46 301 4 1-cyclopropyl-2-oxo-6- (trifluoromethyl)-3H- benzimidazole-4-carboxylic I-6 acid 0.99 287 3 methyl 1-cyclopropyl-6- (difluoromethoxy)-2-oxo- 3H-benzimidazole-4- I-11 carboxylate 0.85 299 1 1-cyclopropyl-6- (difluoromethoxy)-2-oxo- 3H-benzimidazole-4- I-12 carboxylic acid 0.74 285 1 1-cyclopropyl-6- (difluoromethyl)-2-oxo-3H- benzimidazole-4-carbonyl fluo 251 I-39 ride 0.98 [M-F]+ [0454] Abbreviations used in synthesis schemes and preparatory examples ACN acetonitrile CPME cyclopentyl methyl ether (or methoxy cyclopentane) Boc t-butoxycarbonyl DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCM dichloromethane 109921 | 83192 FF DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DMA N,N-dimethylacetamide DMF N,N-dimethylformamide DMF-DMA N,N-dimethylformamide dimethyl acetal DMSO dimethyl sulfoxide DMSO-d6 deuterated dimethylsulfoxide DPEN diphenylethylenediamine Et3N triethylamine EtOAc ethyl acetate EtOH ethanol HATU (1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) HCl hydrochloric acid MeOH methanol Ms methanesulfonyl (mesyl) NaHCO3 sodium hydrogen carbonate NaOH sodium hydroxide nBu, tBu n-butyl, t-butyl NH4Cl ammonium chloride NPhth phthalimide-1-yl OMs mesylate group OTf triflate group OTs tosylate group PdCl2dppf 1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride PyBOP benzotriazol-1-yloxy)tripyrrolidino-phosphonium hexafluorophosphate T3P® propanephosphonic acid cyclic anhydride TBME tert-butyl methyl ether TEA triethylamine TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl Tf trifluoromethanesulfonyl (triflyl) TFA trifluoroacetic acid THF tetrahydrofuran Ts p-toluenesulfonyl (tosyl) XPhos 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl aq. aqueous °C degrees Celsius equiv. equivalent 109921 | 83192 FF h hour(s) LC/MS or LCMS liquid chromatography mass spectrometry M molar MHz megahertz min minutes mp or M.P. melting point NMR nuclear magnetic resonance ppm parts per million RT room temperature Rt retention time Biological Examples [0455] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm. Example B1: Activity against Chilo suppressalis (Striped rice stemborer) [0456] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. [0457] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36, P37, P38, P39, P40, P41, P42, P43, P48, P49, P51, P54, P56, P57. Example B2: Activity against Diabrotica balteata (Corn root worm) [0458] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation. [0459] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P5, P6, P7, P9, P10, P11, P16, P17, P18, P19, P20, P21, P24, P25, P27, P28, P34, P35, P37, P38, P40, P41, P44, P48, P49, P51, P52, P53, P54, P55, P57. Example B3: Activity against Euschistus heros (Neotropical Brown Stink Bug) 109921 | 83192 FF [0460] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. [0461] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P6, P7, P9, P10, P11, P16, P19, P20, P21, P25, P29, P31, P34, P35, P38, P40, P41, P42, P44, P48, P49, P50, P51, P53, P54, P57. Example B4: Activity against Frankliniella occidentalis (Western flower thrips). Feeding/Contact activity [0462] Bean leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 4 days after infestation. [0463] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P2, P6, P7, P10, P13, P16, P19, P21, P24, P25, P27, P32, P34, P38, P39, P41, P44, P48, P49. Example B5: Activity against Myzus persicae (Green peach aphid). Intrinsic activity [0464] Test compounds prepared from 10'000 ppm DMSO stock solutions were applied by pipette into 24- well microtiter plates and mixed with a nutrient solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation. [0465] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P30, P31, P32, P33, P34, P35, P37, P38, P39, P40, P41, P42, P48, P49, P50, P51, P53, P54, P55, P56. Example B6: Activity against Myzus persicae (Green peach aphid). Feeding/Contact activity [0466] Eggplant leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation. [0467] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P2, P16, P20, P21, P41, P51, P57.
109921 | 83192 FF Example B7: Activity against Plutella xylostella (Diamond back moth) [0468] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation. [0469] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36, P37, P38, P39, P40, P41, P42, P43, P44, P45, P46, P47, P48, P49, P51, P52, P53, P54, P55, P56, P57. Example B8: Activity against Spodoptera littoralis (Egyptian cotton leaf worm) [0470] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. [0471] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P9, P10, P11, P13, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P7, P38, P39, P40, P41, P43, P45, P48, P49, P51, P52, P54, P55, P57. Example B9: Comparison of the insecticidal activity of compounds P2, P16 and P38 according to the invention with a structurally most closely comparable compound from the state of the art: [0472] Activity of compounds P2, P16 and P38 according to the preparatory examples and of a compound from WO 19/197468 against Spodoptera littoralis (Example B8 above), Chilo suppressalis (Example B1 above), Diabrotica balteata (Example B2 above), Plutella xylostella (Example B7 above) and Euschistus heros (Example B3 above) is summarized in Table B9. Table B9: Concentration Mortality Compound Insect (ppm) (%) Present invention – Compound P2 200 Spodoptera littoralis 100 200 Chilo suppressalis 100 200 Diabrotica balteata 100 200 Plutella xylostella 100 200 Euschistus heros 100 109921 | 83192 FF Concentration Mortality Compound Insect (ppm) (%) Present invention – Compound P16 200 Spodoptera littoralis 100 200 Chilo suppressalis 100 200 Diabrotica balteata 100 200 Plutella xylostella 100 200 Euschistus heros 100 Present invention – Compound P38 200 Spodoptera littoralis 100 200 Chilo suppressalis 100 200 Diabrotica balteata 100 200 Plutella xylostella 100 200 Euschistus heros 100 State of the art – Described in WO 19/197468 200 Spodoptera littoralis 0 as compound I-108 (page 180) 200 Chilo suppressalis 0 200 Diabrotica balteata 0 200 Plutella xylostella 0 200 Euschistus heros 0 [0473] Table B9 shows that compounds P2, P16 and P38 according to the invention exert a substantially better insecticidal action on Spodoptera littoralis, Chilo suppressalis, Diabrotica balteata, Plutella xylostella and Euschistus heros than the compound from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds. Example B10: Comparison of the insecticidal activity of compound P16 according to the invention with structurally most closely comparable compounds from the state of the art: [0474] Activity of compound P16 according to the preparatory examples and of compounds from WO 20/094363 against Spodoptera littoralis (Example B8 above), Plutella xylostella (Example B7 above) and Euschistus heros (Example B3 above) is summarized in Table B10. 109921 | 83192 FF Table B10: Concentration Mortality Compound Insect (ppm) (%) Present invention – Compound P16 50 Spodoptera littoralis 100 12.5 Plutella xylostella 80 12.5 Euschistus heros 100 State of the art – Described in WO 50 Spodoptera littoralis 80 20/094363 as compound P-18 (page 91) 12.5 Plutella xylostella 50 12.5 Euschistus heros 0 State of the art – Described in WO 50 Spodoptera littoralis 0 20/094363 as compound P-7 (page 89) 12.5 Plutella xylostella 0 12.5 Euschistus heros 0 [0475] Table B10 shows that compound P16 according to the invention exert a substantially better insecticidal action on Spodoptera littoralis, Plutella xylostella and Euschistus heros than the compounds from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds. Example B11: Comparison of the insecticidal activity of compound P49 according to the invention with a structurally most closely comparable compound from the state of the art: [0476] Activity of compound P49 according to the preparatory examples and of a compound from WO 21/069575 against Spodoptera littoralis (Example B8 above), Diabrotica balteata (Example B2 above) and Euschistus heros (Example B3 above) is summarized in Table B11. 109921 | 83192 FF Concentration Mortality Compound Insect (ppm) (%) Present invention – Compound P49 200 Spodoptera littoralis 100 50 Diabrotica balteata 80 200 Euschistus heros 80 State of the art – Described in WO 200 Spodoptera littoralis 0 21/069575 as compound I-20 (page 151) 50 Diabrotica balteata 0 200 Euschistus heros 0 [0477] Table B11 shows that compound P49 according to the invention exerts a substantially better insecticidal action on Spodoptera littoralis, Diabrotica balteata and Euschistus heros than the compound from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds.

Claims

109935 | 83192 FF1. A compound of the formula (I) wherein A is CH or N; X is an oxygen atom or a sulfur atom; the staggered line represents the connection of Q to the rest of compound of the formula (I); R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a is hydrogen, C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3- C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, cyano, C1-C3alkyl, and C1-C3haloalkyl; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4 is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo- pyridazinyl optionally N-substituted with a single substituent R4c; R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10 ; 109935 | 83192 FF R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of the compound of formula (I). 2. The compound according to claim 1, wherein A is CH. 3. The compound according to claim 1 or 2, wherein X is oxygen. 4. The compound according to any one of claims 1 to 3, wherein R1 is hydrogen, methyl, or cyclopropylmethyl. 5. The compound according to any one of claims 1 to 4, wherein R2a is hydrogen, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl or 1-cyanocyclopropyl; and R2b is halogen, C1-C3fluoroalkyl, C1- C3fluoroalkoxy, or cyclopropyl. 6. The compound according to any one of claims 1 to 5, wherein R3 is methyl. 7. The compound according to any one of claims 1 to 6, wherein. - Q is Qa and R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, or Qc-9; or - Q is Qb and R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, Qc-9, Qc-10, or Qc-11: R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, difluoromethyl, methoxy, ethoxy, - C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10 or -N(CH3)C(O)R10; and 109935 | 83192 FF R4c is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl. 8. The compound according to any one of claims 1 to 7, wherein R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or cyanomethyl, preferably, R10 is hydrogen, methyl, or cyanomethyl; and R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy, preferably, R11 is hydrogen or methyl. 9. The compound according to any one of claims 1 to 8, wherein R4 is 5-cyano-2-pyridyl, pyrimidin-2- yl,5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6- (difluoromethyl)pyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (dimethylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6- [cyanomethyl(methyl)carbamoyl]pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 6- methoxypyridazin-3-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6- oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5-carbamoyl-thiazol-2-yl; and R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl. 10. The compound according to any one of claims 1 to 9, wherein R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy; and R5a and R5b are hydrogen. 11. A composition comprising a compound as defined in any one of claims 1 to 10, one or more auxiliaries and diluent, and optionally one or more other active ingredient. 12. A method (i) of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in any one of claims 1 to 10, or of a composition as defined in claim 11; or (ii) for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the plant propagation material or the site where the propagation material is planted, with an effective amount of a compound as defined in any one of claims 1 to 10, or of a composition as defined in claim 11; or (iii) of controlling parasites in or on an animal in need thereof, comprising administering an effective amount of a compound as defined in any one of claims 1 to 10, or of a composition as defined in claim 11. 13. A plant propagation material, such as a seed, comprising, or coated with, or treated with, or adhered thereto, a compound as defined in any one of claims 1 to 10, or a composition as defined in claim 11. 14. A compound of the formula IIa-1, or of the formula IIa-2: 109935 | 83192 FF wherein A, R2a and R2b are as defined in claim 1, 2 and 5; and Ra is C1-C6alkyl or benzyl; the following compounds being excluded: - 2,3-Dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - Methyl 2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Methyl 6-fluoro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - 2,3-Dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylic acid, - Methyl 2,3-dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 2,3-dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylate, - 2,3-Dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylic acid, - 6-Bromo-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 2,3-Dihydro-2-oxo-6-(trifluoromethyl)-1H-benzimidazole-4-carboxylic acid, - 1-Ethyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - Methyl 1-ethyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - 2,3-Dihydro-6-methoxy-2-oxo-1H-benzimidazole-4-carboxylic acid, - 6-Chloro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 6-Fluoro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - Ethyl 2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Methyl 6-chloro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 6-chloro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 6-fluoro-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 6-bromo-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - 1-(2-Fluoro-1-methylethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic , - Methyl 6-chloro-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate acid, - Ethyl 6-bromo-1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 6-bromo-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 6-chloro-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate, - Methyl 6-bromo-1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylate, - Ethyl 2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate, - Methyl 2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate, - 6-Bromo-2,3-dihydro-1-(1-methylethyl)-2-oxo-1H-benzimidazole-4-carboxylic acid, - 6-Bromo-1-cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, 109935 | 83192 FF - Methyl 6-bromo-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylate, - 1-(3-Fluoropropyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 2,3-Dihydro-2-oxo-1-(2,2,3,3-tetrafluoropropyl)-1H-benzimidazole-4-carboxylic acid, - 1-(2-Fluoroethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 6-Bromo-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylic acid, - 6-Chloro-2,3-dihydro-1-methyl-2-oxo-1H-benzimidazole-4-carboxylic acid, - 2,3-Dihydro-2-oxo-1-(2,2,2-trifluoroethyl)-1H-benzimidazole-4-carboxylic acid, - 2,3-Dihydro-1-(1-methylpropyl)-2-oxo-1H-benzimidazole-4-carboxylic acid, - 1-Cyclobutyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 1-(2,2-Difluoroethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 1-(1,1-Dimethylethyl)-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 2,3-Dihydro-2-oxo-1-propyl-1H-benzimidazole-4-carboxylic acid, - 1-Cyclopropyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid, - 2,3-Dihydro-1-(2-methylpropyl)-2-oxo-1H-benzimidazole-4-carboxylic acid, and - 1-Butyl-2,3-dihydro-2-oxo-1H-benzimidazole-4-carboxylic acid. 15. A compound according to claim 14, wherein A is CH.
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